BIOLOGY 

LIBRARY 


ORGANIC  COMPOUNDS 
OF   MERCURY 


BY 


FRANK  C.  WHITMORE,  PH.D. 

PROFESSOR  OF   ORGANIC   CHEMISTRY, 
NORTHWESTERN   UNIVERSITY 


American  Chemical  Society 
Monograph  Series 


BOOK  DEPARTMENT 
The  CHEMICAL  CATALOG  COMPANY,  Inc. 

ONE  MADISON  AVENUE,  NEW  YORK,  U.  S.  A. 
1921 


COPYRIGHT,  1921,  BY 
The  CHEMICAL  CATALOG  COMPANY,  Inc. 

All  Rights  Reserved 


81OLOGY 
LIBRARY 





Press  of 

J.   J.   Little  &  Ives  Company 
New  York,  U.   S.   A. 


GENERAL   INTRODUCTION 

American  Chemical   Society   Series   of 
Scientific  and  Technologic  Monographs 

By  arrangement  with  the  Interallied  Conference  of  Pure  and  Ap- 
plied Chemistry,  which  met  in  London  and  Brussels  in  July,  1919,  the 
American  Chemical  Society  was  to  undertake  the  production  and  pub- 
lication of  Scientific  and  Technologic  Monographs  on  chemical  subjects. 
At  the  same  time  it  was  agreed  that  the  National  Research  Council, 
in  cooperation  with  the  American  Chemical  Society  and  the  American 
Physical  Society,  should  undertake  the  production  and  publication  of 
Critical  Tables  of  Chemical  and  Physical  Constants.  The  American 
Chemical  Society  and  the  National  Research  Council  mutually  agreed 
to  care  for  these  two  fields  of  chemical  development.  The  American 
Chemical  Society  named  as  Trustees,  to  make  the  necessary  arrange- 
ments for  the  publication  of  the  monographs,  Charles  L.  Parsons, 
Secretary  of  the  American  Chemical  Society,  Washington,  D.  C.; 
John  E.  Teeple,  Treasurer  of  the  American  Chemical  Society,  New 
York  City;  and  Professor  Gellert  Alleman  of  Swarthmore  College. 
The  Trustees  have  arranged  for  the  publication  of  the  American  Chem- 
ical Society  series  of  (a)  Scientific  and  (b)  Technologic  Monographs 
by  the  Chemical  Catalog  Company  of  New  York  City. 

The  Council,  acting  through  the  Committee  on  National  Policy 
of  the  American  Chemical  Society,  appointed  the  editors,  named  at 
the  close  of  this  introduction,  to  have  charge  of  securing  authors,  and 
of  considering  critically  the  manuscripts  prepared.  The  editors  of 
each  series  will  endeavor  to  select  topics  which  are  of  current  interest 
and  authors  who  are  recognized  as  authorities  in  their  respective  fields. 
The  list  of  monographs  thus  far  secured  appears  in  the  publisher's 
own  announcement  elsewhere  in  this  volume. 

The  development  of  knowledge  in  all  branches  of  science,  and 
especially  in  chemistry,  has  been  so  rapid  during  the  last  fifty  years 
and  the  fields  covered  by  this  development  have  been  so  varied  that 

3 


^48994 


4       .  GENERAL  INTRODUCTION 

it  is  difficult  for  any  individual  to  keep  in  touch  with  the  progress  in 
branches  of  science  outside  his  own  specialty.  In  spite  of  the  facilities 
for  the  examination  of  the  literature  given  by  Chemical  Abstracts 
and  such  compendia  as  Beilstein's  Handbuch  der  Organischen  Chemie, 
Richter's  Lexikon,  Ostwald's  Lehrbuch  der  Allgemeinen  Chemie, 
Abegg's  and  Gmelin-Kraut's  Handbuch  der  Anorganischen  Chemie  and 
the  English  and  French  Dictionaries  of  Chemistry,  it  often  takes  a 
great  deal  of  time  to  coordinate  the  knowledge  available  upon  a  single 
topic.  Consequently  when  men  who  have  spent  years  in  the  study 
of  important  subjects  are  willing  to  coordinate  their  knowledge  and 
present  it  in  concise,  readable  form,  they  perform  a  service  of  the 
highest  value  to  their  fellow  chemists. 

It  was  with  a  clear  recognition  of  the  usefulness  of  reviews  of  this 
character  that  a  Committee  of  the  American  Chemical  Society  recom- 
mended the  publication  of  the  two  series  of  monographs  under  the 
auspices  of  the  Society. 

Two  rather  distinct  purposes  are  to  be  served  by  these  mono- 
graphs. The  first  purpose,  whose  fulfilment  will  probably  render  to 
chemists  in  general  the  most  important  service,  is  to  present  the 
knowledge  available  upon  the  chosen  topic  in  a  readable  form,  in- 
telligible to  those  whose  activities  may  be  along  a  wholly  different 
line.  Many  chemists  fail  to  realize  how  closely  their  investigations 
may  be  connected  with  other  work  which  on  the  surface  appears  far 
afield  from  their  own.  These  monographs  will  enable  such  men  to 
form  closer  contact  with  the  work  of  chemists  in  other  lines  of  re- 
search. The  second  purpose  is  to  promote  research  in  the  branch  of 
science  covered  by  the  monograph,  by  furnishing  a  well  digested  sur- 
vey of  the  progress  already  made  in  that  field  and  by  pointing  out 
directions  in  which  investigation  needs  to  be  extended.  To  facilitate 
the  attainment  of  this  purpose,  it  is  intended  to  include  extended  ref- 
erences to  the  literature,  which  will  enable  anyone  interested  to  follow 
up  the  subject  in  more  detail.  If  the  literature  is  so  voluminous  that 
a  complete  bibliography  is  impracticable,  a  critical  selection  will  be 
made  of  those  papers  which  are  most  important. 

The  publication  of  these  books  marks  a  distinct  departure  in  the 
policy  of  the  American  Chemical  Society  inasmuch  as  it  is  a  serious 
attempt  to  found  an  American  chemical  literature  without  primary 
regard  to  commercial  considerations.  The  success  of  the  venture  will 
depend  in  large  part  upon  the  measure  of  cooperation  which  can  be 
secured  in  the  preparation  of  books  dealing  adequately  with  topics 


GENERAL  INTRODUCTION  5 

of  general  interest;  it  is  earnestly  hoped  therefore  that  every  member 
of  the  various  organizations  in  the  chemical  and  allied  industries  will 
recognize  the  importance  of  the  enterprise  and  take  sufficient  interest 
to  justify  it. 


AMERICAN   CHEMICAL   SOCIETY 

BOARD    OF    EDITORS 

Scientific  Series:—  Technologic  Series:— 

WILLIAM  A.  NOTES,  Editor,  JOHN  JOHNSTON,  Editor, 

GILBERT  N.  LEWIS,  C.  G.  DERICK, 

LAFAYETTE  B.  MENDEL,  WILLIAM  HOSKINS, 

ARTHUR  A.  NOTES,  F.  A.  LIDBURT, 

JULIUS  STTEGLITZ.  ARTHUR  D.  LITTLE, 

C.  L.  REESE, 
C.  P.  TOWNSEND. 


American  Chemical  Society 

MONOGRAPH   SERIES 

Other  monographs  in  the  series  of  which  this  book  is  a  part 
are  now  ready  or  in  process  of  being  printed  or  written.  They 
will  be  uniform  in  size  and  style  of  binding.  The  list  up  to 
July  First,  1921,  includes: 

The  Animal  as  a  Converter. 

By  HENRY  PRENTISS  ARMSBY.    About  250  to  300  pages. 
The  Chemistry  of  Enzyme  Actions. 

By  K.  GEORGE  FALK.    136  pages.    Now  ready. 
The  Properties  of  Electrically  Conducting  Systems. 

By  CHARLES  A.  KRAUS.    About  400  pages,  illustrated. 
Carotinoids  and  Belated  Pigments:  The  Chromolipins. 

By  LEROY  S.  PALMER.    About  200  pages,  illustrated. 
Thyroxin.      By  E.  C.  KENDALL. 
The  Properties  of  Silica  and  the  Silicates. 

By  ROBERT  S.  SOSMAN.    About  500  pages,  illustrated. 
The  Chemical  Effects  of  Alpha  Particles  and  Electrons. 

By  SAMUEL  C.  LIND.    182  pages.    Now  ready. 
Coal  Carbonization. 

By  HORACE  C.  PORTER.    About  475  pages,  illustrated. 
The  Corrosion  of  Alloys.     By  C.  G.  FINK. 
Industrial  Hydrogen.  By  HUGH  S.  TAYLOR.    About  200 

pages. 

The  Vitamines.    By  H.  C.  SHERMAN.    About  200  pages. 
Piezo- Chemistry.   By  L.  H.  ADAMS.    About  350  pages. 
Cyanamide.    By  JOSEPH  M.  BRAHAM. 
Liquid  Ammonia  as  a  Solvent.     By  E.  C.  FRANKLIN. 
Wood  Distillation.      By  L.  F.  HAWLEY. 
Shale  Oil.    By  RALPH  H.  McKEE. 
Alumino thermic  Reduction  of  Metals.  By  B.  D.  SAKLAT- 

WALLA. 
The  Analysis  of  Rubber.      By  JOHN  B.  TUTTLE.     About 

225  pages. 
Zirconium     and    Its     Compounds.      By  F.  P.  VENABLE. 

About  300  pages. 
The    Chemistry    of    Leather    Manufacture.      By  JOHN 

A.  WILSON.    About  400  to  500  pages. 

For  additional  information  regarding  this  series  of  monographs,  see 
General  Introduction,  page  3.  As  the  number  of  copies  of  any  one 
monograph  will  be  limited,  advance  orders  are  solicited. 

The  CHEMICAL  CATALOG  COMPANY,  Inc. 

ONE  MADISON  AVENUE,  NEW  YORK,  U.  S.  A. 


AUTHOR'S  PREFACE 

Organic  compounds  of  mercury  have  been  studied  by  many  in- 
vestigators from  1850  to  the  present  time.  The  interest  in  these  sub- 
stances has  increased  in  recent  years  because  of  the  need  for  some 
non-ionized  mercury  compound  for  use  with  the  organic  arsenicals  in 
the  treatment  of  syphilis.  The  total  amount  of  work  which  has  been 
done  on  organic  mercury  compounds  is  probably  greater  than  that 
done  on  the  arsenicals  but  it  has  received  much  less  publicity.  Al- 
though a  number  of  monographs  have  been  written  in  English  and  in 
German  on  the  arsenic  compounds  none  has  appeared  in  any  language 
on  the  mercurials. 

Originally  the  writer  hoped  to  include  in  the  present  monograph 
all  of  the  organic  compounds  which  contain  mercury  in  any  form.  It 
soon  became  evident  that  the  work  could  not  be  all-inclusive.  Atten- 
tion will  therefore  be  confined  almost  entirely  to  the  true  organic 
mercury  compounds  in  which  mercury  is  attached  directly  to  carbon. 
These  substances  have  practically  none  of  the  properties  of  mer- 
curic salts.  The  0  —  Hg  compounds  such  as  the  salts  of  the  organic 
acids,  the  N  —  Hg  compounds  such  as  the  mercury  acid  amide  com- 
pounds, and  the  S  —  Hg  compounds  such  as  the  mercuric  mercaptides 
will  be  touched  on  very  lightly  as  most  of  their  properties  are  the 
properties  of  inorganic  mercury  salts.  The  great  mass  of  biological 
and  pharmacological  studies  which  have  been  made  on  organic  mer- 
curials will  not  be  included  both  because  of  lack  of  space  and  because 
of  the  unsatisfactory  condition  of  the  literature  of  this  phase  of  the 
subject.  Another  subject  of  considerable  interest  which  cannot  be  dis- 
cussed is  the  host  of  "double  compounds"  of  mercury  compounds  and 
organic  substances.  These  subjects  which  are  not  discussed  are  made 
available  for  further  study  by  the  supplementary  bibliographical  lists 
in  the  Appendix.  In  this  way  the  writer  has  attempted  to  include  in 
one  form  or  another  all  of  the  material  which  has  been  gathered  in  the 
preparation  of  the  work. 

The  monograph  will  be  arranged  to  serve  both  the  general  chemist 
who  wishes  to  get  a  conception  of  what  has  been  done  in  the  field  as 

7 


8  AUTHOR'S  PREFACE 

a  whole  and  the  specialist  who  wishes  to  find  out  quickly  what  has  been 
done  in  any  particular  portion  of  the  field.  In  many  cases  unsettled 
points  have  been  indicated.  It  is  hoped  that  the  work  will  inspire 
further  research  in  this  interesting  field.  It  has  been  found  necessary 
to  omit  practically  all  detailed  experimental  material.  In  general 
enough  detail  is  given  to  make  evident  the  method  but  not  enough  to 
serve  as  a  laboratory  guide  in  repeating  any  of  the  work.  The  lists 
of  references  given  in  the  text  contain  the  most  important  articles  on 
the  given  subject.  Many  of  the  less  important  references  have  been 
omitted  but  will  be  found  in  the  supplementary  bibliographical  lists. 

The  writer  has  a  number  of  acknowledgments  to  make.  Portions  of 
the  work  have  been  done  with  aid  from  the  libraries  of  the  following 
institutions,  University  of  Chicago,  University  of  Minnesota,  Univer- 
sity of  Wisconsin,  Abbott  Laboratories,  and  the  John  Crerar  Library 
of  Chicago.  Valuable  suggestions  have  been  received  from  Professors 
Roger  Adams,  W.  Lee  Lewis,  and  A.  S.  Loevenhart.  Dr.  Austin  M. 
Patterson  has  made  many  helpful  suggestions  for  naming  organic 
mercury  compounds.  Mr.  Edmund  B.  Middleton,  Research  Assistant 
under  the  U.  S.  Interdepartmental  Social  Hygiene  Board,  has  rendered 
invaluable  assistance  in  arranging  and  checking  the  bibliographical 
material  and  in  reading  the  proof. 

F.  C.  W. 

NORTHWESTERN  UNIVERSITY, 
Evanston,  Illinois. 


CONTENTS 

PAGE 

CHAPTER  I.     HISTORICAL  OUTLINE        ...  .  13 

CHAPTER  II.     GENERAL  METHODS  OF  PREPARING  ORGANIC  MER- 
CURY COMPOUNDS 26 

I.     From  organic  halides 26 

II.     Mercuration  by  mercuric  oxide  .         .        .        .        .30 

III.  Addition  to  unsaturated  compounds  ....  31 

IV.  Mercuration  of  halogenated  acetylenes  and  ethylenes  34 
V.     Mercuration   of   aromatic    compounds   by   mercuric 

acetate 34 

VI.     Replacement  of  certain  acid  groups  by  mercury         .       37 

CHAPTER  III.     GENERAL  PROPERTIES  AND  REACTIONS  OF  ORGANIC 

MERCURY  COMPOUNDS 38 

I.     Reaction  with  acids '  .41 

II.    Reaction  with  bases   .        .        .        .  .        .       47 

III.  Reaction  with  inorganic  sulfides        ....       50 

IV.  Change    from    compounds    RHgX,    to    compounds 

R2Hg 59 

V.  Reaction  of  compounds  R2Hg  with  mercuric  salts  .  65 

VI.  Reaction  with  halogens      .        .        .        ..       .        .  67 

VII.  Reaction  with  halides  and  cyanides  of  metals        .  73 

VIII.  Reaction  with  halides  of  non-metals    .       ...       .  78 

IX.  Reaction  with  organic  halides  .        ...        .79 

X.  Reaction  with  metals         .        .        .        .        .        .  83 

CHAPTER  IV.    ALKYL  MERCURY  COMPOUNDS       .        .        .        .85 

• 
CHAPTER  V.    MERCURY  COMPOUNDS  OBTAINED  FROM  OLEFINES 

AND  ACETYLENES 107 

CHAPTER  VI.    MERCURY  COMPOUNDS  FROM  SATURATED  AND  UN- 
SATURATED  ALCOHOLS 125 

CHAPTER  VII.    MERCURY  DERIVATIVES  OF  FATTY  ACIDS  AND  RE- 
LATED COMPOUNDS 137 

9 


10  CONTENTS 

PAGE 

CHAPTER  VIII.    MERCURY    DERIVATIVES    OF    ALDEHYDES,    KE- 

TONES,  AMIDES,  AND  RELATED  COMPOUNDS    .        .154 

CHAPTER  IX.  MERCURY  DERIVATIVES  OF  AROMATIC  HYDROCAR- 
BONS AND  NITRO  COMPOUNDS 163 

CHAPTER  X.    MERCURY  DERIVATIVES  OF  AROMATIC  AMINES       .     205 

CHAPTER  XI.     MERCURY  DERIVATIVES  OF  PHENOLS,  NAPHTHOLS, 

AND  RELATED  COMPOUNDS 254 

CHAPTER  XII.    MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS        .     290 

CHAPTER  XIII.     MERCURY  DERIVATIVES  OF  AROMATIC  KETONES, 

TERPENES,  AND  RELATED  COMPOUNDS    .        .        .     324 

CHAPTER  XIV.  MERCURY  DERIVATIVES  OF  HETEROCYCLIC  COM- 
POUNDS, Azo  COMPOUNDS,  AND  AROMATIC  ARSENI- 
CALS  .  . 333 

APPENDIX  A.    ANALYSIS  OF  ORGANIC  MERCURY  COMPOUNDS       .     361 
APPENDIX  B.    LIST  OF  PROPRIETARY  MERCURIALS        .        .        .     368 

APPENDIX  C.  BIBLIOGRAPHY  OF  BIOLOGICAL  AND  PHARMACO- 
LOGICAL WORK  WITH  ORGANIC  MERCURY  COM- 
POUNDS   371 

APPENDIX  D.    SUPPLEMENTARY  BIBLIOGRAPHICAL  LISTS     .        .     373 

APPENDIX  E.  LIST  OF  PATENTS  DEALING  WITH  ORGANIC  MER- 
CURY COMPOUNDS 378 

INDICES  .  381 


TO 

CHARLES  LORING  JACKSON 


ORGANIC  COMPOUNDS  OF 
MERCURY 

Chapter  I. 

Historical  Outline  of  the   Study  of  Organic  Mercury 
.     Compounds. 

In  1843  A.  W.  von  Hofmann  obtained  a  mercury  compound  from 
aniline  and  mercuric  chloride.1  To  this  day  it  is  not  certainly  known 
whether  this  product  had  mercury  attached  to  nitrogen  or  to  carbon. 
If  the  latter  is  true  this  substance  was  the  first  compound  containing 
the  C  —  Hg  linkage.  In  1850  Frankland  noted  that  ethyl  iodide  re- 
acts with  metallic  mercury  in  sunlight  giving  gaseous  products.2  Two 
years  later  he  found  that  methyl  iodide  reacts  with  mercury  in  sun- 
light forming  the  crystalline  organomercuric  compound,  methyl  mer- 
curie  iodide. 


Soon  other  chemists  turned  their  attention  to  mercury  alkyl  com- 
pounds. In  1854  Strecker  made  ethyl  mercuric  iodide  by  treating  ethyl 
iodide  with  metallic  mercury  in  diffused  light.5  He  converted  the 
iodide  into  other  ethyl  mercuric  salts.  In  the  same  year  Diinhaupt 
obtained  ethyl  mercuric  chloride  by  heating  bismuth  triethy  1  with  mer- 
curic chloride.6  Later  Buckton  made  an  extensive  study  of  other 
methyl  and  ethyl  mercuric  compounds.7 

In  1851  Sobrero  and  Selmi  had  introduced  another  type  of  organic 
mercury  compound.8  By  heating  mercuric  chloride  and  potassium 

»Ann.  47   (1843),  62. 

«J.  Chem.  Soc.  3   (1850),  322.     Ann.  77   (1851),  225. 

•Ann.  85  (1853),  361. 

*  Those  less  familiar  with  organic  mercury  compounds  should  note  that  the  alkyl 
mercuric  halides  resemble  the  analogous  Barbier-Grignard  reagents  in  formula  only. 
The  physical  and  chemical  properties  of  the  two  classes  of  compounds  are  entirely 
different. 

s  Ann.  92  (1854),  75. 

«J.  prakt.  Ch&m.  (1)  61  (1854),  423.  Ann.  92  (1854),  379. 

'Ann.  108  (1858),  103;  109  (1859),  219;  112  (1859),  220. 

"Ann.  80  (1851),  108. 

13 


14  "e<  ^  COMPOUNDS  OF  MERCURY 

hydroxide:}^  ^JedhpJ  they  (/ot-'ined  a  yellow  slightly  explosive  sub- 
stance containing  'mercury  and  carbon.  Many  of  their  contemporaries 
tried  without  success  to  make  this  explosive  compound.  Their  work 
is  of  interest  only  as  a  forerunner  of  the  extensive  work  of  K.  A. 
Hofmann  on  the  mercarbides,  compounds  containing  the  grouping, 

Hg  — 
/ 

-C-Hg- 
\ 

Hg- 

In  1855  Zinin  found  that  allyl  iodide  unites  with  metallic  mercury 
forming  a  crystalline  compound  even  more  rapidly  than  does  methyl 
iodide.9 

CH2  =  CH  -  CH2 1  +  Hg  ->  CH2  =  CH  -  CH2  -  Hg  - 1. 

The  method  of  making  alkyl  mercury  compounds  by  introducing 
mercury  directly  into  alkyl  iodides  is  very  limited  as  only  a  few  com- 
pounds give  the  reaction.  A  new  and  more  general  method  of  prepara- 
tion was  devised  by  Frankland  and  Duppa  in  1863.10  They  found  that 
methyl  and  ethyl  iodides  react  with  sodium  amalgam  in  the  presence 
of  ethyl  acetate  forming  mercury  dimethyl  and  mercury  diethyl. 

2  CH3  - 1  +  Hg  +  2  Na  -»  2  Nal  +  CH3  -  Hg  -  CH3. 
At  this  time  Frankland  studied  the  action  of  the  mercury  alkyls  with 
various  metals  thus  obtaining  a  number  of  other  metal  alkyls.  In 
1866  Chapman  improved  Frankland's  method  for  making  mercury 
alkyls  by  using  bromides  instead  of  iodides.11  At  this  time  Schorlem- 
mer  recommended  the  action  of  sulfuric  acid  with  mercury  diethyl  for 
making  pure  ethane.12 

2  (C2H5)  2Hg  +  H2S04  -»  2C2H6  +  (C2H5  -  Hg)  2S04. 
In  1868  Otto  treated  bromonaphthalene  with  sodium  amalgam  to 
prepare  dinaphthyl  but  instead  obtained  mercury  dinaphthyl.13  He 
extended  Frankland's  reaction  to  the  aromatic  series,  and  made  a  very 
careful  study  of  the  reactions  of  organic  mercury  compounds  in  gen- 
eral. Among  the  reactions  which  he  studied  are  the  following:  the 
action  of  acids  to  form  hydrocarbons  and  organomercuric  salts;  the 

9  Ann.  96  (1855),  363. 

10  J.  Chem.  Soc.  16  (1863),  415.  Ann,.  130  (1864),  104. 

11 J.  Chem.  Soc.  19  (1866),  150.  Ann.  139  (1866),  128.' 

12  Ann.  132  (1864),  234. 

"Ann.  147  (1868),  164;  154  (1870),  188. 


HISTORICAL  OUTLINE  OF  MERCURY  COMPOUNDS      15 

action  of  halogens  to  form  organic  halides  and  organomercuric  halides 
or  mercuric  halides;  with  mercuric  salts  to  form  organomercuric  salts; 
and  with  oxidizing  agents  to  form  organomercuric  hydroxides.  It  is 
noteworthy  that  the  compounds  R  —  HgOH  have  strongly  basic  prop- 
erties. These  general  reactions  may  be  summarized  by  the  following 
equations: 


R-Hg-R  +  HgX2-»2R-Hg-X  14      . 
R_  Hg-  R  +  KMn04  -»  R-  Hg-  OH 

Dreher  and  Otto  next  studied  mercury  diphenyl  and  mercury  ditolyl, 
prepared  by  the  action  of  sodium  amalgam  and  ethyl  acetate  on  bromo- 
benzene  and  p-bromotoluene.15  They  discovered,  however,  a  limita- 
tion to  Frankland's  reaction  when  they  tried  to  prepare  mercury  di- 
benzyl  from  benzyl  bromide  and  sodium  amalgam. 

Mercury  dibenzyl  has  since  been  prepared  but  only  by  means  of 
the  Grignard  reagent.16 

In  1869  Wurtz  treated  chloroformic  ester  and  bromobenzene  with 
sodium  amalgam.  Besides  ethyl  benzoate  he  obtained  a  by-product  of 
mercury  diphenyl.17  In  a  similar  way  he  obtained  mercury  ditolyl 
as  a  by-product  of  the  action  of  sodium  amalgam  on  a  mixture  of 
chloroformic  ester  and  p-bromotoluene. 

In  1871  Reynolds  first  studied  the  action  of  mercuric  salts  and  alkali 
on  acetone.18  Although  the  complex  mercury  compounds  obtained  in 
this  way  have  been  studied  by  a  number  of  investigators  their  struc- 
ture is  not  yet  established.  In  1873  Cahours  prepared  and  studied  the 
mercury  derivatives  of  propyl  and  isobutyl.19  The  next  year  Victor 

14  This  is  one  of  the  most  striking  and  general  reactions  of  the  organic  mercury 
compounds,  in  which  both  bonds  of  the  mercury  are  attached  to  carbon.  Usually  the 
reaction  is  brought  about  by  the  simple  mixing  of  solutions  of  R2Hg  and  the  mercuric 
salt.  In  a  few  cases  heat  is  required.  In  general  the  product  of  the  reaction, 
R  —  Hg  —  X,  is  more  insoluble  than  the  compound  R2Hg  or  the  mercuric  salt.  How- 
ever, this  insolubility  does  not  seem  to  be  the  controlling  cause  of  the  change  as  the 
same  reaction  takes  place  in  some  instances  in  which  R^Hg  is  the  more  insoluble. 

16  .Ber.  2  (1869),  542.  Ann.  154  (1870),  93,  171.  J.  praJct.  Chem.  (2)  1  (1870), 
179. 

16  Pope  and  Gibson,  J.  CJiem.  800.  101  (1912),  735.  Wolff,  Ber.  46  (1913),  64. 
Hilpert  and  Griittner,  Ber.  48  (1915),  906.  L.  W.  Jones,  J.  Am.  Chem.  Soc.  40  (1918), 
1257. 

"Compt.  rend.  68  (1869)  1298.    Ann.  Spl.  7  (1870),  124. 

185er.  4   (1871),  483. 

w€ompt.  rend.  76  (1873),  134;  77  (1873),  1405.  J.  prakt.  Ohem.  (2)  8  (1873), 
397. 


16  COMPOUNDS  OF  MERCURY 

Meyer  made  a  mercury  compound  from  nitromethane.  Although 
this  substance  is  not  a  true  organic  mercury  compound,  in  that  the  mer- 
cury is  attached  to  oxygen,  it  is  mentioned  because  it  played  so  im- 
portant a  part  in  the  study  of  the  structure  of  fulminic  acid.20  At  this 
time  Ladenberg  found  that  mercury  diphenyl  reacts  with  silicon  tetra- 
chloride  giving  a  phenyl  silicon  compound.21 

SiCl4  +  C6H5  -  Hg  -  C6H5  -»  C6H5  -  Hg  -  Cl  +  C6H5  -  SiCl3. 

In  1876  Michaelis  published  the  first  results  of  his  study  of  the 
aromatic  compounds  of  the  nitrogen  group.22  He  first  used  mercury 
diphenyl  and  phosphorus  trichloride. 

PC13  +  C6H5  -  Hg  -  C6H5  -»  C.H.  -  Hg  -  Gl  +  C6H5  -  PCI,. 
These  studies  were  continued  with  results  of  the  utmost  importance 
to  the  study  of  organic  arsenicals.  In  1880  Oppenheim  made  the  first 
mercury  derivative  of  acetoacetic  ester.23  In  1880  Michaelis  treated 
mercury  diphenyl  with  arsenious  chloride,  obtaining  two  reactions,  de- 
pending on  the  conditions.24 

AsCl3  +  C6H5  -  Hg  -  C6H5  -»  C6H5  -  Hg  -  Cl  +  C6H3  -  AsCU. 
2AsCl3  +  C6H5  -  Hg  -  CrH5  -»  HgCl2  +  2C6H5  -  AsCl2. 

In  the  same  year  Kutscheroff  studied  the  effect  of  mercuric  salts  on 
allylene  and  acetylene.25  The  mercury  compounds  obtained  are  de- 
composed by  acids  giving  the  hydration  products  of  the  acetylene 
compounds,  in  these  casefc,  acetone  and  acetaldehyde. 

Acid 

CH3  —  C  =  CH >  Mercury  compound.       — »  CH3  —  CO  —  CH3 

Acid 

CH  =  CH         — >  Mercury  compound.       — >  CH3  —  CO  —  H. 

In  spite  of  the  fact  that  some  fifteen  chemists  have  published  work 
on  the  subject,  the  structure  of  the  mercury  compounds  obtained 
from  acetylene  is  not  yet  settled.  However  the  reaction  has  acquired 
considerable  commercial,  importance  as  it  gives  the  means  of  convert- 
ing acetylene  into  alcohol  and  acetic  acid.  At  this  time  Michaelis 
contributed  a  new  reaction  to  the  chemistry  of  organic  mercury  by  the 

20 Meyer,  Ann.  171   (1874),  81.    •  Ber.  5   (1872),  516.     Nef,  Ann.  280   (1894),  263. 
L.  W.  Jones,  Am.  Chem.  J.  20  (1898),  33. 
21  Ann,  173  (1874),  151. 
**Ann.  181   (1876),  288. 
28  Ber.  10  (1877),  701. 
»-Ann.  201  (1880),  184. 
26  Ber.  13  (1880),  17;  14  (1881),  1536;  17  (1884),  13. 


HISTORICAL  OUTLINE  OF  MERCURY  COMPOUNDS      17 

discovery  that  aromatic  boric  acids  react  with  mercuric  chloride  solu- 
tion, giving  aromatic  mercuric  chlorides.26 
C6H5  -  B  (OH)2  +  HgCl2  +  H20  ->  C6H5  -  Hg  -  Cl  +  H3B03  +  HCL 

A  few  years  later  Michaelis  extended  Frankland's  reaction  beyond  the 
range  of  hydrocarbon  derivatives,  by  treating  p-bromodimethylaniline 
with  sodium  amalgam  and  ethyl  acetate.27  This  reaction  gave  him  a 
new  type  of  mercury  compound  from  which  he  made  new  aromatic 
derivatives  of  the  nitrogen  group  of  elements. 

2  (CH3)  2N  -  C6H4  -  Br  +  Hg  +  2Na  -> 
2NaBr  +  (CH3)  2N  -  C6H4  -  Hg  -  C6H4  -  N  (CH.)  2 

Michaelis  next  extended  the  reaction  to  phenol  ethers  using  p-bromo- 
anisole  and  sodium  amalgam  in  the  presence  of  ethyl  acetate.28 

In  1892  Pesci  published  the  first  of  his  many  researches  on  the 
mercury  derivatives  of  aniline  and  its  substitution  products.29  Before 
this  time  he  had  been  working  on  ammonia  mercuric  compounds.  This, 
without  doubt,  led  to.  his  study  of  aniline  mercury  compounds  and 
likewise  to  his  misinterpretation  of  their  structures  and  reactions.30  In 
spite  of  these  errors,  Pesci 's  work  has  been  of  the  greatest  importance 
in  the  development  of  the  chemistry  of  organic  mercury.  He  was  the 
first  to  realize  that  mercury  could  be  introduced  into  the  nucleus  of 
an  aromatic  amine.  Interpreted  in  modern  formulas,  Pesci's  reaction 
between  dimethylaniline  and  mercuric  acetate  becomes, 
(CH.)  2N  -  C6H5  +  Hg (OAc)  2  ->  (CH3)  2N  -  C^  -  HgOAc  +  HOAc. 

Although  he  misinterpreted  the  reaction,  he  made  a  careful  study  of 
the  methods  of  changing  compounds  of  the  type  R  —  Hg  —  X  to  those 
of  the  type  R2Hg  in  which  both  bonds  of  mercury  are  attached  to 
carbon.  The  reagents  which  he  used  most  frequently  were  sodium 
sulfide  and  sodium  thiosulfate.  Again  using  the  correct  formulas,  one 
of  these  reactions  may  be  represented  by  the  equation 

2(CH3)2N-C6H4-HgOAc  +  2Na2S203->Na2Hg(S203)2  + 
[(CH3)2N-C6H4-]2Hg. 

The  compound  obtained  in  this  case  proved  to  be  identical  with  the 
product  obtained  by  Michaelis  from  sodium  amalgam  and  p-bromo- 

"Ber.  15  (1882),  180. 

*Ber.  21  (1888),  1501;  23  (1890),  2342.     Ann.  260   (1890),  6. 
*Ann.  293  (1896),  196,  313. 

nAtti  acad.  Lincei  (5)  II  (1892),  312.     Gazz.  chim.  ital.  22  I   (1892),  373.     Ghent. 
Zentr.  1892  II  213.    Z.  anorg.  Chem.  15   (1897),  208;  17  (1898),  276. 
30  Cf.  J.  Am.  Chem.  Soc.  41  (1919),  1842. 


18  COMPOUNDS  OF  MERCURY 

dimethylaniline.  This  identity  proves  that  the  mercuration  of  the 
aromatic  amine  with  mercuric  acetate  takes  place  in  the  para  posi- 
tion to  the  dimethyl-amino  group. 

In  the  same  year  that  Pesci  made  his  discovery,  Volhard  independ- 
ently discovered  the  direct  replacement  of  hydrogen  by  mercury.  He 
found  that  thiophene  reacts  with  mercuric  salts,  giving  a  product  hav- 
ing mercury  in  the  alpha  position.31 

CH  =  CH  CH  =  CH 


|  >S  +  Hg01af+NaOAc-»  |  >S  +  NaCl  +  HOAc. 

CH  =  CH  CH  =  C  —  HgCl 

In  1894  Desesquelle  prepared  mercury  derivatives  of  phenols  and 
naphthols.32  He  misinterpreted  the  structure  of  many  of  these  sub- 
stances by  assuming  that  the  mercury  must  be  attached  to  oxygen.  In 
all  probability  it  is  attached  to  carbon  and  they  are  therefore  true 
organic  mercury  compounds.  In  1897  Bamberger  discovered  a  new  re- 
action of  organic  mercury  compounds  when  he  treated  mercury  di- 
phenyl  with  nitrous  anhydride  obtaining  benzene  diazonium  nitrate.33 

(C6H5)  2Hg  +  2N203  ->  C6H5  -  Hg  -  N03  +  C6H5  -  N  -  N03. 

N 

He  applied  this  reaction  to  mercury  dimethyl,  hoping  to  obtain  an  ali- 
phatic diazonium  compound,  but  instead,  he  obtained  imidodihydrox- 
imic  acid, 

OH 


NH 


In  1898  Dimroth  first  showed  that  mercuration 34  of  aromatic  com- 
pounds is  as  general  a  process  as  nitration  or  sulfonation.  Pesci's  work 

81  Awn.  267   (1892),  172. 

**Bull.  soc.  chim.   (3)  11  (1894),  263. 

™Ber.  30  (1897),  509;  31  (1898),  1528;  32  (1899),  3546.  Cf.  Chem.  Zentr.  1898 
II  1015. 

3*  Some  chemists  prefer  the  longer  term  "mercurization."  Apparently  the  only 
authority  for  this  is  found  in  Patterson's  "German-English  Dictionary  for  Chemists" 
in  which  "merkurieren"  is  translated  "mercurize."  Undoubtedly  this  is  a  more  literal 
translation  of  the  German  word  than  "mercurate."  Dr.  Patterson  in  a  private  com- 


HISTORICAL  OUTLINE  OF  MERCURY  COMPOUNDS       19 

had  been  confined  to  the  aromatic  amines  and  his  interpretation  of  the 
reactions  had  been  faulty.  Dimroth  showed  that  mercuric  acetate  in- 
troduces the  acetoxymercuri  group,  —  HgOAc,  into  a  great  variety  of 
aromatic  compounds  including  hydrocarbons,  phenols,  and  nitroben- 
zene.35 He  interpreted  all  of  the  reactions  correctly,  and  showed  the 
errors  in  Pesci's  work.  Some  of  Dimroth's  results  may  be  illustrated 

by  the  equations  — 

110° 
C6H6  +  Hg  (OAc)  2  ---  >  C6H5  -  HgOAc  +  HOAc. 

Reflux 

CH3  -  C6H5  +  Hg  (OAc)  2  --  >  CH:{  -  C6H4  -  HgOAc  +  HOAc. 

Mixture  of  o-  and  p- 

Cold 

C6H5  -  NH2  +  Hg(OAc)2  -     -^  AcOHg  -  C6H4  -  NH2  +  HOAc. 


Alcohol  o_    and   p_ 

Cold 

C6H5  -  OH  +  Hg  (OAc)  2  -     —  »  AcOHg  -  C6H4  -  OH 

water     Mixture  of  o-  and  p- 
+  (  AcOHg)  2C6H3  -  OH  +  HOAc. 
o,  p-Compound. 

Reflux 

C6H5  -  N02  +  Hg  (OAc)  2  --  >  AcOHg  -  C6H4  -  N02  +  HOAc. 

ortho  compound. 

It  will  be  noticed  that  the  mercuration  reactions  follow  the  ordinary 
rules  for  orientation  except  in  the  case  of  nitrobenzene.  It  is  a  gen- 
eral fact  that  groups  like  the  nitro  and  carboxyl  groups,  which  usually 
direct  the  entering  group  to  the  meta  position,  are  mercurated  in  the 
ortho  position  instead. 

In  the  same  year  that  Dimroth  published  his  first  results,  K.  A. 
Hofmann  started  his  study  of  the  mercarbides,  compounds  in  which 
all  of  the  hydrogens  of  a  methyl  group  are  replaced  by  mercury.36 
Ethyl  alcohol  yields  ethane  hexamercarbide. 

0  —  Hg  Hg  —  0 

NaOH  +  yellow  HgO  \       \          /       / 

C2H5OH    -  -->  Hg  —  C  —  C  —  Hg 

Heated.  /          \ 

HO  —  Hg  Hg  —  OH 

munication  expresses  a  slight  preference  for  the  form  of  the  verb,  "to  mercurate." 
This  form  is  used  because  it  suggests  the  similarity  of  the  process  to  those  reactions 
which  are  indicated  by  the  verbs  "to  brominate,"  "to  nitrate,"  etc.  Moreover  "mer- 
curize"  suggests  the  pharmacist's  processes  involving  the  physical  incorporation  of 
materials  with  metallic  mercury. 

^Ber.'  31  (1898),  2154;  32  (1899),  758.  Habilitationsschr.  Tubingen  (1900), 
Chem.  Zentr.  1901  I  449-454.  Ber.  35  (1902),  2044,  2853. 

**Ber.  31  (1898),  2624;  33  (1900),  1328;  38   (1905),  3654. 


20  COMPOUNDS  OF  MERCURY 

Bamberger  prepared  mercury  derivatives  of  beta-naphthol  by  means 
of  mercuric  acetate.  He  also  discovered  that  diazonium  salts  react 
with  mercurated  phenols  replacing  the  mercury  by  the  benzeneazo 
group  if  the  mercury  occupies  the  position  normally  involved  in  the 
coupling  reactions  of  the  free  phenol.37  This  reaction  may  be  illus- 
trated by  the  equations  involving  mercurated  phenols  later  studied  by 
Dimroth. 

OH  OH 

]    +C6H5-N2-C1 >    |       |+HgCl2 


HgCl  N  =  N-C6H5. 

Part  of  the  coupling  takes  place  in  the  ortho  position  giving  a  small 
amount  of  an  azo  compound  still  containing  mercury, 

OH 


HgCl 

If  the  position  in  which  the  coupling  takes  place  is  unsubstituted 
the  coupling  is  completed  without  the  removal  of  the  mercury  from 
the  nucleus.  Thus  an  ortho-mercurated  phenol  would  give  a  com- 
pound, 

OH 

-HgCl 


=  N  —  CH. 


In  1899  Deniges  published  a  classification  of  mercury  compounds 
and  the  results  of  a  study  of  the  action  of  mercuric  salts  on  ethylene 
compounds.38 

In  1900  Hofmann  and  Sand  published  the  first  of  a  lengthy  series 
of  papers  on  the  action  of  mercuric  salts  with  ethylene  and  other  un- 
saturated  compounds.39  Biilmann  disagreed  with  some  of  the  results 
obtained  by  these  investigators.40  In  general  the  reaction  of  a  mer- 
curic salt  with  an  ethylene  compound  in  the  presence  of  water,  con- 

87  Ber.  31  (1898),  2624. 

**Ann.  chim.  phys.  (7)  18  (1899),  382-432.     Bull.  soc.  chim.  (3)   19  (1898),  494. 

"Bcr.  33    (1900),  1340,  1358,  2692;  34    (1901),  1385,  2906. 

*°Ber.  33   (1900),  1641;  35  (1902),  2586. 


HISTORICAL  OUTLINE  OF  MERCURY  COMPOUNDS      21 

sists  in  the  addition  of  the  groups  —  OH  and  —  HgX  to  the  double 
bond.  Various  more  complicated  compounds  are  also  obtained.  The 
simplest  reaction  is  as  follows: 

CH2  =  CH2  +  Hg(NO3)2  +  H2O  ->  HN03  +  CH2  —  CH2 


)H       HgN03 

In  1901  Pesci 40a  replaced  a  carboxyl  group  by  mercury  by  heating 
phthalic  acid  with  mercuric  acetate.  The  reaction  probably  takes 
place  as  follows: 

0 

V— C  — 0 
\TTcr      Heat 
OXH         Hg(OAc) 
—  C  — O 

0 

'\  —  C  =  0 

+  co, 


Pesci  did  not  realize  that  this  reaction  could  be  extended  to  the  prepa- 
ration of  other  mercury  compounds.  Recently  Kharasch  has  extended 
this  reaction  to  a  great  variety  of  compounds  making  available  types 
of  mercury  compounds  which  can  be  obtained  in  no  other  way.40b 

In  1902  Balbiano  and  Paolini,  while  using  mercuric  acetate  solu- 
tion as  an  oxidizing  agent,  discovered  that  it  gives  mercury  derivatives 
with  the  allyl  compounds  of  phenol  ethers.    The  reaction  with  a  sub- 
stance like  safrol  consists  in  the  addition  of  the  groups  — OH  and 
-  HgOAc  to  the  double  bond.41 

CH202C6H3  —  CH2  —  CH  =  CH2 > 


CH202C6H3  —  CH2  —  CH  —  CH2 

OH      HgOAc 

The  corresponding  propenyl  compounds  such  as  isosafrol  give  no  mer- 
cury compounds  but  undergo  oxidation  with  the  formation  of  glycols. 

*°*RAL.  (5)  10  I  (1901),  362. 

«b  private  communication,  M'.  S.  Kharasch,  University  of  Chicago. 

*lBer.  35  (1902),  2994;  36   (1903),  3575. 


22  COMPOUNDS  OF  MERCURY 

The  group  —  CH  =  CH  — CH,   changes  to  —  CHOH  — CHOH- 

CH{  and  mercurous  acetate  precipitates. 

In  1904  Pfeiffer  and  Truskier  applied  the  Grignard  reagent  to  the 
preparation  of  organic  mercury  compounds.42  They  prepared  mercury 
diphenyl  from  phenyl  magnesium  bromide  and  mercuric  chloride  ac- 
cording to  the  equation, 

2C6H5  -  Mg  -  Br  +  HgCl2  -»  C«HB  -  Hg  -  C0H5  +  HgBr2  +  MgCl2. 
The  next  year  Peters  discovered  a  new  preparation  of  aromatic  mer- 
cury compounds  by  heating  a  sulfinic  acid  with  mercuric  chloride.43 

C6H5  -  S02H  +  HgCl2  -»  C0Hr,  -  Hg  -  Cl  +  S02  +  HC1. 
In  1908  Hantzsch  and  Auld  published  a  study  of  the  mercury  deriva- 
tives of  nitro  phenols.44  This  work  gave  some  interesting  results  bear- 
ing upon  the  relation  between  quinoid  structure  and  color.  Tafel 
discovered  a  new  method  for  making  certain  mercury  dialkyls  during 
some  experiments  on  the  reduction  of  ketones  in  acid  solution  with  a 
mercury  cathode.  The  reduction  of  acetone  and  methyl  ethyl  ketone 
gives  mercury  di-isopropyl  and  mercury  di-secondary-butyl.45  The 
formation  of  the  latter  substance  may  be  represented  as  follows: 

CH3  CH3  CH3 

\  \  / 

2  C  =  0  +  Hg  +  6(H)^  CH  — Hg  — CH          +  2H.O. 

/  /  \ 

C2H5  C2H5  C2H5 

In  1907  Emil  Fischer  made  beta-mercury  dipropionic  acid  by  ap- 
plying Frankland's  sodium  amalgam  reaction  to  beta-iodopropionic 
ester.46  He  was  unable  to  obtain  mercury  derivatives  from  alpha 
halogen  esters.  Hofmann  and  Kirmreuther  found  that  halogenated 
acetylenes  and  ethylenes  having  only  one  hydrogen  atom  can  be 
changed  to  organic  mercury  compounds  by  simple  treatment  with  an 
alkaline  solution  of  mercuric  cyanide.47  Trichloroethylene  acts  as 
follows : 
2C12C  =  CHC1 •+  Hg(CN)2  +  2KOH  -»  2KCN  +  (C12C  =  CCl)2Hg. 

In  1908  Schoeller  and  Schrauth  published  the  first  of  their  long 
series  of  papers  covering  almost  all  types  of  organic  mercury  com- 

42  Ber.  37  (1904),  1125. 

43  Ber.  38  (1905),  2567. 
*4Ber.  39  (1906),  1105. 
<*Ber.  39  (1906),  3626. 
46  Ber.  40  (1907),  386. 

« Ber.  41  (1908),  314;  42  (1909),  4232. 


HISTORICAL  OUTLINE  OF  MERCURY  COMPOUNDS      23 

pounds.  Their  first  study  was  on  mercury  malonic  ester  and  its  hy- 
drolysis.48 Biilmann  discovered  that  allocinnamic  acid  gives  an  or- 
ganic mercury  compound  with  mercuric  acetate,  whereas  common 
cinnamic  acid  does  not.49  The  product  is  an  inner  salt  or  anhydride 
of  a-hydroxymercuri-(3-hydroxy-hydrocinnamic  acid.  As  in  the  case 
of  the  ethylene  hydrocarbons  the  reaction  consists  in  the  addition  of  the 
hydroxyl  and  hydroxymercuri  groups  to  the  double  bond.  In  1910 
Schoeller  and  Schrauth  applied  Biilmann's  discovery  of  the  action  of 
mercuric  acetate  with  allocinnamic  acid  to  methyl  cinnamate.  In 
methyl  alcohol  solution  a  compound  is  formed  which  has  a  methoxy 
group  and  an  acetoxymercuri  group  added  to  the  double  bond.50 

<T,H5  —  CH  =  CH  —  C02CH3  +  Hg(OAc)2  +  CH3OH 

->  C6H5  —  CH  —  CH  —  C02CH3  +  HOAc 


OCH,  H 


gOAc 

In  the  next  few  years  they  extended  their  studies  to  the  mercury  com- 
pounds of  alpha-anilino  acids,51  toluidines  and  toluidides,52  anthranilic 
esters,53  and  pyrazolones.54  They  also  found  that  ethylene  reacts  with 
an  alcoholic  solution  of  mercuric  acetate  much  as  does  methyl  cinna- 
mate.55 

CH9   —  CH2 

+  HOAc 

)CH3      HgOAc 


v^ 

<L 


In  1913  Kraus  electrolyzed  solutions  of  alkyl  mercuric  halides  in 
liquid  ammonia.  He  obtained  a  number  of  the  free  radicals  or  com- 
plex metals,  R  —  Hg — ,56  He  found  them  to  be  unstable,  readily 
changing  to  free  mercury  and  a  mercury  dialkyl  when  allowed  to  warm 
up  to  room  temperature.  In  the  same  year  von  Braun  studied  the  ac- 
tion of  sodium  amalgam  on  dibromides  and  obtained  compounds  con- 
taining mercury  as  a  member  of  a  heterocyclic  ring.57  An  example 
of  these  substances  is  the  compound  obtained  -from  pentamethylene  di- 

18  Ber.  41  (1908),  2087. 

48 Ber.  41  (1908),  4340.     Ber.  43  (1910),  568. 

60  Ber.  43  (1910),  695;  44   (1911),  1048,  1432. 

61  Ber.  44  (1911),  1300. 

62  Ber.  45  (1912),  2808. 

63  Ber.  47  (1914),  1930. 

64  Ber.  47  (1914),  2736. 
KBer.  46  (1913),  2864. 

66  J.  Am.  Chem.  Soc.  35   (1913),  1732. 

67  Ber.  46   (1913),  1792;  47    (1914),  490. 


24  COMPOUNDS  OF  MERCURY 

GEL  — CH2 
/  \ 

bromide,  CH2  Hg.    These  substances  are  hard  to  obtain 

\  / 

CH2  — CH2 

in  monomolecular  form  as  they  polymerize  readily.  Hilpert  and  Dit- 
mar  found  that  aluminum  carbide  can  be  used  with  mercuric  chloride 
to  form  methyl  mercuric  chloride  or  mercury  dimethyl.58  Hilpert  and 
Griittner  studied  "mixed"  mercury  alkyls  and  aryls  in  which  the  two 
bonds  of  the  mercury  are  attached  to  different  hydrocarbon  residues. 
These  substances  are  extraordinarily  unstable,  readily  changing  to  a 
mixture  of  the  two  simple  compounds,  R2Hg  and  R'2Hg.59  In  this 
same  year  Brieger  and  Schulemann  published  an  extended  study  of 
the  mercuration  of  the  naphthalene  intermediates  of  the  coal-tar  dye 
industry.  In  many  cases  they  were  unable  to  obtain  mercurated  prod- 
ucts as  the  intermediates  were  oxidized  by  the  mercuric  salts.60  In 
1916  Grignard  and  Abelmann  applied  the  Grignard  reaction  to  mer- 
curated ketones,  obtaining  mercurated  tertiary  alcohols.61  In  1918 
L.  W.  Jones  published  a  paper  on  the  electronic  nature  of  the  C  —  Hg 
bonds  in  the  mercury  dialkyls  and  similar  compounds.62  He  advanced 
evidence  to  show  that  the  two  benzyl  groups  in  mercury  dibenzyl  are 
of  opposite  charge,  as  they  are  removed  by  hydrolysis  in  the  form 

of  toluene  and  benzyl  alcohol  respectively.    This  would  indicate  that 
+  — 

the  mercury  atom  is  Hg,  at  least  at  the  instant  splitting  takes  place.63 
This  is  in  harmony  with  the  fact  that  the  mercury  appears  as  the  free 
metal  at  the  end  of  the  reaction.  In  1920  Kharasch  and  Piccard  pub- 
lished preliminary  results  on  the  preparation  of  some  dyes  containing 
mercury.64  Manchot  has  recently  published  a  series  of  papers  to 
prove  that  the  many  organic  mercury  compounds  obtained  from  un- 
saturated  compounds  are  mere  molecular  compounds  having  no  struc- 
tural relation  between  the  unsaturated  carbon  atoms  and  the  groups 
—  HgX  and  —  OH  or  —  OR  which  appear  in  the  products.65  The  sim- 
plest compound  of  ethylene  with  a  mercuric  salt  would  thus  be 

**Ber.  46  (1913),  3738. 

»Ber.  47   (1914),  177,  186. 

«°J.  prakt.  Ohem.  (2)  89  (1914),  97. 

61  Bull.  soe.  chim.  (4)  19  (1916),  18. 

««7.  Am.  Chem.  Soc.  40   (1918),  1257. 

88  Compare  Kharasch,  J.  Am.  Chem.  Soc.  43  (1921),  May  ?. 

•*  J.  Am.  Ohem.  Soc.  42  (1920),  1861. 

wBer.  53  (1920),  984.    Ann.  421  (1920),  316,  331. 


HISTORICAL  OUTLINE  OF  MERCURY  COMPOUNDS      25 

(XH4.Hg(OH)X.  Much  more  experimental  work  must  be  forthcom- 
ing before  the  problem  of  the  true  nature  of  these  compounds  is 
settled. 

Recently  Kharasch  66  has  shown  that  acids  which  lose  carbon  di- 
oxide readily  on  heating  form  mercuric  salts  which  also  lose  carbon 
dioxide  on  heating.  Compounds  of  the  type  R2Hg  are  usually  obtained. 
The  reaction  has  been  applied  to  a  great  variety  of  mercuric  salts.  It 
may  be  illustrated  by  the  following  case: 


86  Private  communication. 


Chapter  II. 

General  Methods  of  Preparing  Organic  Mercury 
Compounds. 

I.    Preparation  from  Organic  Halides. 

Among  the  many  general  methods  for  the  introduction  of  mercury 
into  organic  compounds  are  the  three  following,  each  of  which  starts 
with  an  organic  halide;  the  action  of  free  mercury  on  an  alkyl  iodide, 
the  action  of  sodium  amalgam  on  an  organic  iodide  or  bromide,  and  the 
action  of  a  mercuric  halide  on  a  Grignard  reagent. 

A.  Reaction  of  Metallic  Mercury  with  Alkyl  Iodides. 

In  this  reaction  the  iodide  adds  to  the  mercury  giving  a  substance 
which  has  one  bond  of  the  mercury  attached  to  carbon  and  the  other 
attached  to  iodine.  Thus  methyl  iodide  reacts  readily  with  metallic 
mercury  in  sunlight  giving  a  crystalline  mass  of  methyl  mercuric  iodide. 

CH3-I  +  Hg-^CH3-Hg-I. 

When  ethyl  iodide  is  used  the  reaction  must  be  carried  out  in  diffused 
light  as  direct  sunlight  decomposes  ethyl  mercuric  iodide.  The  higher 
alkyl  iodides  probably  react  much  more  slowly  with  mercury  but  no 
accurate  study  of  the  subject  has  been  made.  The  bromides  and  chlo- 
rides do  not  react  with  metallic  mercury  in  this  way.  The  unsatu- 
rated  iodides,  allyl  iodide  and  propargyl  iodide,  unite  with  mercury 
even  more  readily  than  methyl  iodide  forming  the  compounds 
CH2  =  CH  —  CH2  —  Hgl  and  CH  =  C  —  CH2  —  Hgl.  Methylene 
iodide  rapidly  forms  iodomethyl  mercuric  iodide,  I  —  CH2  —  Hgl,  or 
methylene  mercuric  iodide,  CH2(HgI)2,  depending  on  the  amount  of 
mercury  used. 

B.  Reaction  of  Sodium  Amalgam  with  Organic  Iodides  and  Bromides. 

The  product  of  this  reaction  differs  from  that  obtained  from  me- 
tallic mercury  in  having  both  bonds  of  the  mercury  attached  to  car- 
bon. The  reaction  takes  place  only  in  the  presence  of  an  ester  like 

26 


METHODS  OF  PREPARING  MERCURY  COMPOUNDS      27 

methyl  or  ethyl  acetate.  At  the  end  of  the  reaction  the  ester  can  be 
recovered  unchanged.  There  is  no  satisfactory  explanation  for  this 
catalytic  action  of  the  ester.  Methyl  iodide  reacts  rapidly  with  cold 
very  dilute  sodium  amalgam  forming  mercury  dimethyl. 

2CH3  -  I  +  2Na  +  Hg  ->  CH3  -  Hg  -  CH3  +  2NaI. 

This  reaction  takes  place  very  readily  in  the  aliphatic  series.  The 
best  yields  are  obtained  at  a  low  temperature  with  amalgams  con- 
taining only  about  0.1  per  cent  of  sodium.  Jn  the  aromatic  series  more 
concentrated  amalgams  and  higher  temperatures  must  be  used. 

In  the  aliphatic  series  the  reaction  has  been  used  with  bromides  or 
iodides  of  methyl,  ethyl,  n-propyl,  isobutyl,  isoamyl,  and  octyl.  Sec- 
ondary iodides  react  vigorously  with  sodium  amalgam  but  form  no  or- 
ganic mercury  compounds.  The  mercury  secondary  alkyls  which 
would  be  expected  have  only  been  obtained  as  by-products  in  the  reduc- 
tion of  ketones  in  acid  solution  with  a  mercury  cathode.  In  this  way 
acetone  and  methyl  ethyl  ketone  give  small  amounts  of  mercury  di- 

CH3 

/ 
isopropyl,     Hg(  —  CH1          )2,      and      mercury      di-secondan/-butyl, 

CH3 
CH3 

/ 
Hg(  —  CH          )2.    The  failure  to  obtain  these  substances  by  the  so- 


dium  amalgam  method  may  be  due  to  their  easy  change  to  the  ro^™- 
sponding  hydrocarbons.  There  is  one  case,  however,  in  which  a  sec- 
ondary iodide  gives  an  organic  mercury  compound.  Cyclohexyl  iodide 
reacts  with  sodium  amalgam  forming  cyclohexyl  mercuric  iodide  in- 
stead of  the  expected  mercury  di-cyclohexyl.  Apparently  the  sodium 
does  not  take  part  in  the  reaction. 

The  reaction  of  several  aliphatic  dihalides  with  sodium  amalgam 
has  been  studied.  Ethylene  dibromide  and  trimethylene  dibromide 
react  but  give  no  organic  mercury  compounds.  Tetramethylene  di- 
iodide  and  pentamethylene  dibromide  or  di-iodide  react  more  vigorously 
with  dilute  sodium  amalgam  than  does  methyl  iodide.  The  products 
are  compounds  containing  mercury  as  a  member  of  a  heterocyclic  ring. 
Pentamethylene  dibromide  gives  three  isomeric  products  having  the 


28  COMPOUNDS  OF  MERCURY 

composition  C5H10Hg  and  molecular  weights  corresponding  to  one, 
four,  and  six  of  these  simple  molecules.  The  simplest  substance  is  a 

CH2  — CH2 

/  \ 

six  membered  ring  containing  mercury,  CH2  Hg.    The  ten- 

\  / 

CH2  —  CH2 

dency  of  this  substance  to  polymerize  resembles  that  of  the  cyclic 
ethers  and  sulfides. 

In  the  aromatic  series  the  sodium  amalgam  reaction  has  been  used 
with  monobromobenzene  and  the  bromides  of  a  great  variety  of  ben- 
zene homologs.  These  include  almost  all  of  the  possible  methyl,  di- 
methyl, and  trimethyl  benzenes  as  well  as  n-propyl  benzene,  p-cymene, 
and  pentamethyl  benzene.  The  products  are  mercury  diphenyl  and 
its  homologs.  Mono-  and  dibromodiphenyls  give  very  insoluble  mer- 
cury compounds  which  have  not  been  carefully  studied.  The  a  and 
p-naphthyl  bromides  and  iodides  give  the  corresponding  mercury  di- 
naphthyls  when  heated  with  4  per  cent  sodium  amalgam. 

The  reaction  has  been  extended  to  include  halides  other  than  those 
of  the  hydrocarbons.  In  the  aliphatic  series  [3-iodopropionic  ester  gives 
(3-mercury  bis-propionic  ester,  Hg(CH2  —  CH2  —  C02Et)2.  Alpha 
halogen  esters  give  no  mercury  compounds  by  this  reaction.  In  the 
aromatic  series  mercury  compounds  have  been  obtained  from  bromides 
of  dimethyl  aniline,  diethyl  aniline,  dimethyl-p-toluidine,  the  anisoles, 
and  the  phenetoles. 

Many  cases  have  been  observed  in  which  the  action  of  halides  and 
sodium  amalgam  fails  to  give  the  desired  products.  Hydrogen  iodide 
reacts  vigorously  with  sodium  amalgam  in  the  presence  of  ethyl  acetate 
but  gives  no  mercury  hydride.  In  general  an  unusually  active  halide 
does  not  give  a  mercury  compound  with  sodium  amalgam.  Examples 
of  such  compounds  are  alpha  halogen  esters,  benzyl  halides,  and  phen- 
acyl  halides,  C0H5  --  CO  — CH2X.  The  action  of  a  halogen  atom 
attached  to  an  unsaturated  carbon  has  been  studied  in  only  one  case. 
The  compound  C6H5  —  CH  =  C(Br)  —  CH(OAc)  —  CH3  reacts  with 
the  amalgam  but  gives  no  definite  product.1  As  would  be  expected, 
the  sodium  amalgam  reaction  fails  when  applied  to  bromides  contain- 
ing groups  which  react  with  sodium  such  as  the  amino,  hydroxyl, 
nitro,  and  carboxyl  groups.  The  reaction  also  fails  with  chlorides. 

*Sand  and  Singer,  Ber.  35  (1902),  3170. 


METHODS  OF  PREPARING  MERCURY  COMPOUNDS      29 

C.    Reaction  of  Mercuric  Halides  with  the  Grignard  Reagent. 

This  action  takes  place  on  heating  and  gives  a  product  which  has 
one  or  both  bonds  of  the  mercury  attached  to  carbon  depending  on  the 
proportions  of  the  reagents  used. 


I  +  HgI2-*CH3-Hg-I 
2CH3  -  Mg  -  1  +  HgI2  -»  CH3  -  Hg  -  CH3  +  2MgI2. 

In  general  a  much  better  yield  is  obtained  in  the  first  reaction.  This 
method  has  been  little  used  in  the  aliphatic  series  as  the  mercury  alkyls 
have  not  been  studied  much  since  the  introduction  of  the  Grignard  re- 
agent. Mercury  dimethyl  is  most  conveniently  prepared  by  this 
method  using  mercuric  chloride  and  an  excess  of  methyl  magnesium 
iodide.2 

The  Grignard  reagent  obtained  from  pentamethylene  dibromide 
reacts  with  mercuric  bromide  giving  pentamethylene  di-mercuric  bro- 

HgBr 
/ 

mide,  (CH2)5.    A  further  use  of  the  Grignard  reagent  may  be  made 
\ 

HgBr 
by  heating  this  compound  with  phenyl  magnesium  bromide  which  gives 

Hg-C0H5 
/ 
the  complex  compound,  (CH2)5.      This  use  of  a  second  Grignard  re- 

XHg-CfiH5 

agent,  R'  —  Mg  —  X,  on  an  organic  mercuric  halide,  R  —  Hg  —  X, 
does  not  always  produce  the  desired  "mixed"  organic  mercury  com- 
pound R  —  Hg  —  R'.  In  most  cases  the  resulting  product  is  a  mixture 
of  the  two  simple  mercury  compounds  R2Hg  and  R'2Hg.  This  is  the 
case  in  the  action  of  o-tolyl  mercuric  bromide  and  p-tolyl  magnesium 
bromide.  The  "mixed"  compound  expected  is  probably  formed  but 
at  once  changes  to  a  mixture  of  the  simple  substances. 

In  addition  to  these  preparations  the  Grignard  reagent  has  been 
used  to  make  mercury  compounds  of  phenyl,  p-tolyl,  a-naphthyl,  cy- 
clohexyl,  and  benzyl.  It  gives  the  only  means  of  making  mercury 
compounds  of  the  last  mentioned  group. 

The  fact  that  the  Grignard  reagent  does  not  react  with  the  group- 
ing C  —  Hg  —  X  until  heated  makes  it  possible  to  convert  mercurated 

2  Private  coiriiuunicaton  from  C.  S.  Marvel,  University  of  Illinois. 


30  COMPOUNDS  OF  MERCURY 

ketones  to  the  corresponding  mercurated  tertiary  alcohols.    Thus  phen- 
acyl  mercuric  chloride  reacts  with  ethyl  magnesium  bromide  giving  the 
OH 

I 
compound,  C(.H5  —  C  —  CH2  —  HgCl. 

Et 

II.    Mercuration  by  Means  of  Mercuric  Oxide. 

An  entirely  different  method  of  introducing  mercury  into  organic 
compounds  involves  the  action  of  mercuric  oxide,  alone  or  with  a  base, 
on  certain  oxygen  compounds  such  as  alcohols,  ketones,  aldehydes, 
malonic  esters,  and  acetoacetic  ester.  In  the  case  of  ethyl  alcohol 
treatment  with  mercuric  oxide  and  sodium  hydroxide  gives  ethane 
hexamercarbide,  C2Hg6O4H2,  a  mercarbide  being  a  substance  having 
all  the  hydrogen  of  a  methyl  group  replaced  by  mercury.  The  mer- 
carbide just  mentioned  may  be  regarded  as  a  dehydration  product  of 
a  substance  having  six  —  HgOH  groups  attached  to  two  carbon  atoms. 
This  conception  is  strengthened  by  the  fact  that  treatment  with  hydro- 
chloric acid  gives  a  substance  C2Hg6Cl6.  The  structures  of  the  two 
substances  are  thus 

,    0  — Hg  Hg  — 0  Cl  — Hg  Hg  — Cl 

.  \        \        /       /  \          / 

Hg  — C  — C  — Hg        and        Cl  — Hg  — C  — C  — Hg  — Cl 

/        \  /          \ 

HO  — Hg  Hg  — OH  Cl  — Hg  Hg  — Cl 

The  former  compound  on  heating  to  about  230°  changes  color  and 
then  explodes  with  a  brisant  effect  greater  than  that  of  mercury  ful- 
minate. The  hexachloride  is  not  explosive.  Other  mercarbides  and 
less  highly  mercurated  compounds  have  been  obtained  by  the  action  of 
mercuric  oxide  and  a  base  on  aldehydes  and  ketones.  In  most  cases 
the  constitutions  of  these  substances  have  not  been  definitely  estab- 
lished. 

Acetoacetic  ester  and  malonic  esters  react  with  mercuric  oxide  giv- 
ing compounds  having  mercury  substituted  for  hydrogen  of  the  methy- 
lene  group.  Malonic  ester  gives  mercury  bis-malonic  ester.  When  this 
.is  hydrolyzed  and  heated  it  does  not  give  the  expected  mercury  bis- 
acetic  acid  but  gives  an  internal  salt  of  hydroxymercuri 3  acetic  acid, 
HO  —  Hg  —  CH2  —  CO2H.  The  use  of  methyl  malonic  ester  in  a 

3  In  some  cases  the  ordinary  method  of  naming  organic  mercury  salts  as  modified 
mercuric  salts  leads  to  awkward  names.  In  the  above  case  the  ordinary  system  of 


METHODS  OF  PREPARING  MERCURY  COMPOUNDS      31 

similar  series  of  reactions  gives  a  derivative  of  a-mercurated  propionic 
acid.  Thus  these  reactions  make  available  the  alpha  mercurated  com- 
pounds which  cannot  be  made  from  the  alpha-brom  esters  by  the  ordi- 
nary methods.  The  reactions  involved  in  making  the  salts  of  a-hy- 
droxymercuri  propionic  acid  would  be 

CH3          C02Et  CH3          C02Et 

\        /  \        /  NaOH 

C  +HgO  --  >  C  —  > 

/     \  /     \ 

H          CO2Et  HO  —  Hg          CO.Et 

dilute       CH3  -  CH  -  C  =  0 

H2so,  Hg  —  O 

CH3  —  CH  —  C02Na  Naci  CH3  —  CH  —  C  =  O 


Hg  —  Cl  Hg  —  O 

CH3  —  CH  —  C02Na 

HgOH 

III.    Mercuration  of  Unsaturated  Compounds. 

Still  a  third  general  method  for  preparing  organic  mercury  com- 
pounds is  by  treating  unsaturated  compounds  with  mercuric  salts  in 
aqueous  or  alcoholic  solution.  The  reaction  of  an  olefine  compound 
with  an  aqueous  mercuric  salt  consists  in  the  addition  of  the  groups 
-  HgX  and  —  OH  to  the  double  bond.  In  methyl  alcohol  solution 
the  groups  added  are  —  HgX  and  —  OCH3.  Some  authorities  claim 
that  these  addition  products  are  not  true  "structural"  compounds  but 
molecular  compounds  of  one  molecule  of  the  ethylene  compound  and 
one  molecule  of  a  basic  mercuric  salt  or  of  a  hypothetical  substance 

X 

/ 
Hg  .    Neither  of  these  theories  explains  all  of  the  reactions  of 

\ 
OCH3 

the  addition  compounds. 

naming  would  give  "acetic  acid  mercuric  hydroxide,"  "carboxymethyl  mercuric  hy- 
droxide," or  some  other  name  which  is  either  cumbersome  or  fails  to  emphasize  the 
true  nature  of  the  compound.  In  such  cases  it  seems  best  to  give  a  name  to  the  mer- 
cury group,  ^hus  —  IlgOH  is  the  "hydroxymercuri"  group,  —  Hg  —  OAc  is  the  "acetoxy- 
mercuri"  group,  —  HgCl  "chloromercuri,"  etc.  In  a  few  cases  this  system  fails  to  give 
entirely  euphonious  names.  Thus  —  Hg  —  C1O3  must  be  called  the  "chloratemercuri" 
group. 


32  COMPOUNDS  OF  MERCURY 

Ethylene  reacts  with  aqueous  mercuric  salts  under  suitable  con- 
ditions giving  a  mercurated  ethyl  alcohol  or  a  di-mercurated  diethyl 
ether.  The  reactions  may  be  summarized  as  follows: 

CH2  =  CH2  +  HgX2  +  H20  -»  XHg  -  CH2  -  CH2  -  OH  +  HX. 

2CH2  =  CH2  +  2HgX2  +  H20  -» 
XHg  -  CH2  -  CH2  -  O  -  CH2  -  CH2  -  HgX  +  2HX. 

The  mercurated  products  have  been  changed  to  ethyl  alcohol,  ethylene 
iodhydrine,  and  (3[3'-di-iododiethyl  ether.  This  would  settle  the  consti- 
tution of  the  substances  except  for  the  fact  that  both  of  them  react 
with  hydrochloric  acid  or  alkyl  halides  giving  quantitative  yields  of 
ethylene.  The  only  way  to  reconcile  this  formation  of  ethylene  with 
the  structures  used  is  to  assume  that  the  mercury  in  the  grouping 
Hg  —  C  —  C  —  0  has  some  "loosening"  or  "activating"  effect  on 
the  oxygen.  Of  course  the  production  of  ethylene  is  easily  ex- 
plained by  the  "molecular  addition"  formulas,  C2H4.Hg(OH)X  and 
2C2H4.HgO.HgX2.  These,  however,  fail  to  explain  the  other  re- 
actions of  the  substances. 

Methyl  alcohol  solutions  of  mercuric  salts  absorb  ethylene  very 
much  more  rapidly  then  the  aqueous  solutions. 

CH2  =  CH2  +  HgX2  +  CH3OH  ->  XHg  -  CH2  -  CH2  -  OCH3  +  HX. 

The  homologs  of  ethyl  alcohol  give  similar  reactions.  The  mercurated 
products  give  ethylene  with  acids  and  alkyl  halides,  thus  making  pos- 
sible the  formulation  C2H4.Hg(OCH3)X. 

The  reaction  of  aqueous  mercuric  salts  has  been  studied  with 
propylene,  butylene,  and  a  number  of  their  higher  homologs.  Similar 
reactions  take  place  with  allyl  alcohol  and  the  common  unsaturated 
acids.  An  exception  is  found  in  the  case  of  the  trans  isomers  such  as 
fumaric  acid  and  common  cinnamic  acid.  These  substances  give  no 
addition  products  with  mercuric  salts  while  their  cis  isomers,  maleic 
acid  and  allocinnarnic  acid,  readily  add  the  groups  —  HgX  and  —  OH. 

Another  failure  of  this  reaction  is  noted  in  the  case  of  propenyl 
phenyl  derivatives  such  as  isosafrol.  Here  the  mercuric  salt  acts  as  an 
oxidizing  agent  forming  a  glycol. 


CH902  =  CfiH,  —  CH  =  CH  —  CHS 


^/JL-M-OV^O  '         ^-'fi  3  >^y-M.JL V^/J-J.  •s^.m.-B.g 

CH202  =  C6H3  —  CHOH  —  CHOH  —  CH3 
This  is  in  sharp  contrast  to  the  action  of  the  corresponding  allyl  com- 
pounds such  as  safrol  which  add  the  groups  —  HgX  and  —  OH  in  the 


METHODS  OF  PREPARING  MERCURY  COMPOUNDS      33 

usual  way  except  that  two  isomeric  products  are  obtained.  Their  oc- 
currence may  be  due  to  the  addition  of  the  groups  in  the  two  possible 
ways  although  all  other  cases  which  have  been  studied  indicate  that 
this  addition  follows  Markownikoff's  rule,  the  mercury  going  to  the 
carbon  having  the  most  hydrogen  atoms. 

The  addition  of  mercuric  salts  to  double  bonds  takes  place  in  com- 
plicated compounds  in  much  the  same  way  as  it  does  with  ethylene. 
Thus  terpineol  and  the  similar  open  chain  compound,  dimethyl  hep- 
tenol,  give  two  sets  of  compounds,  one  containing  an  —  OH  group  in 
addition  to  the  one  originally  present,  and  the  other  containing  an 
ether  linkage  formed  by  the  elimination  of  water  between  the  two  hy- 
droxyl  groups. 

Various  esters  of  cinnamic  acid  have  been  treated  with  mercuric 
acetate  in  solution  in  methyl,  ethyl,  n-propyl,  and  isopropyl  alcohols. 
The  products  have  the  general  formula  C6H5  —  CH  —  CH  —  CXXR'. 


OR      Hi 


When  treated  with  ammonia  and  hydrogen  sulfide  in  alcohol  solu- 
tion they  give  mercuric  sulfide  and  alkoxyl  hydrocinnamic  esters  of 
the  type  C6H5  —  CH  —  CH2  —  C02R',  a  reaction  which  makes  it  dif- 


)R 

ficult  to  explain  the  mercurated  esters   as  mere  "molecular  com- 
pounds." 

Acetylene,  its  homologs,  and  phenyl  acetylene  react  readily  with 
mercuric  salts.  The  nature  of  the  products  is  still  unsettled  although 
there  is  some  evidence  that  they  contain  a  mercarbide  grouping,  i.e., 
a  completely  mercurated  methyl  group.  Other  investigators  believe 
that  these  products  are  molecular  compounds  of  mercury  acetylides 
and  basic  mercuric  salts.  The  following  explanation  of  the  action  of 
mercuric  chloride  with  acetylene  is  as  plausible  as  any. 

CH  =  CH  -»  ClHg  —  CH  =  CH  —  Cl  -»  (ClHg)  2CH  —  CHC12  -» 
(ClHg)  2CH  —  CHO  ->  (ClHg)  3C  —  CHO. 

Whatever  the  doubt  about  the  structure  of  the  mercury  compounds  it 
is  definitely  established  that  treatment  with  acid  gives  a  hydration 
product  of  the  original  acetylene.  This  change  from  acetylene  to 
acetaldehyde  is  becoming  commercially  important  as  a  step  in  the 
preparation  of  alcohol  and  acetic  acid  from  inorganic  materials. 
Carbon  monoxide  behaves  like  an  unsaturated  compound  with 


34  COMPOUNDS  OF  MERCURY 

mercuric  salts.  When  treated  with  mercuric  acetate  in  alcohol  it 
gives  mercurated  formic  esters  by  the  addition  of  the  —  HgOAc  and 
—  OR  groups.  Reduction  by  amalgamated  aluminum  gives  a  pure 
formic  ester.  Treatment  with  iodine  and  then  with  ammonia  gives 
urethane. 

H  —  C02Et 
/ 
CO->XHg  — C02Et 

\ 

(I  _  C02Et)  -»  NH2  —  C02Et. 

Such  reactions  are  hard  to  explain  on  the  basis  of  molecular  addition 
formulas.  On  the  other  hand  it  is  hard  to  see  from  the  structure  for- 
mulas why  the  mercurated  formic  ester  should  react  with  halogen  acids 
and  alkyl  halides,  giving  carbon  monoxide  quantitatively.  Recent 
work  makes  it  appear  that  this  formation  of  carbon  monoxide  is  a 
property  of  the  grouping  —  Hg  —  C02R.  The  compound, 
Et02C  —  N  —  Hg  —  C02Et 

Et02C  —  N  —  Hg  —  C02Et, 

reacts  with  hydrochloric  acid  giving  exactly  two  molecules  of  car- 
bon monoxide.4 

IV.  Mercuration  of  Halogenated  Acetylenes  and  Ethylenes. 

A  few  unsaturated  compounds  can  be  mercurated  without  involv- 
ing the  multiple  bond.  Such  compounds  are  the  halogenated  ethylenes 
and  acetylenes  which  have  only  one  remaining  hydrogen.  These  sub- 
stances react  with  an  alkaline  solution  of  mercuric  cyanide,  giving  com- 
pounds in  which  both  bonds  of  the  mercury  are  attached  to  carbon. 
Thus  monochloroacetylene  gives  mercury  bis-monochloroacetylene, 
Hg(C  =  C  —  Cl)2,  and  trichloroethylene  gives  a  corresponding  com- 
Cl 

pound,  Hg(  —  C  =  CCL)2.    The  bromine  compounds  have  also  been 
made.    None  of  these  compounds  has  been  carefully  studied. 

V.  Mercuration  of  Aromatic  Compounds. 

The  most  fruitful  method  of  introducing  mercury  into  organic  com- 
pounds has  been  the  direct  mercuration  of  aromatic  compounds  by 
mercuric  acetate.  This  substance  reacts  readily  with  a  great  variety 
of  compounds,  R  —  H,  in  which  R  represents  a  substituted  or  uij- 

*J)iels  and  Utbemann,  B&r.  53  (1920),  725. 


METHODS  OF  PREPARING  MERCURY  COMPOUNDS      35 

substituted  aromatic  residue.  The  process  bears  a  certain  resem- 
blance to  hydrolysis  as  may  be  shown,  by  the  equations 

R  —  H-f  Hg(OAc)2->    R  — HgOAc +  HOAc. 
HO  —  H  +  Hg(OAc)2  ->  HO  —  HgOAc  +  HO  Ac. 

The  analogy  is  borne  out  by  the  fact  that  mercuric  salts  which  do  not 
hydrolyze  do  not  give  the  reaction.  Thus  the  mercuric  halides  give 
no  reaction  in  many  cases  in  which  the  acetate  reacts  with  the  greatest 
ease.  Since  the  mercuric  salts  of  all  of  the  oxygen  acids  are  consider- 
ably hydrolyzed  they  would  be  expected  to  act  like  the  acetate  with 
organic  substances.  Such  is  the  case.  The  acetate,  however,  gives 
the  best  results. 

The  mercuration  of  a  given  aromatic  compound  by  mercuric  acetate 
follows  practically  the  same  course  as  the  bromination  of  the  same 
compound.  Benzene  can  be  mercurated  under  pressure  at  110°  and 
one,  two,  or  even  more  acetoxymercuri  groups  may  be  introduced. 

C6H6  +  Hg(OAc)2  -»  C6H5  -  HgOAc  +  HOAc. 

Toluene  is  mercurated  by  refluxing  with  mercuric  acetate.  The  prod- 
uct is  a  mixture  of  the  o-  and  p-  ring  substituted  compounds.  In 
this  case  the  analogy  to  bromination  fails  as  it  is  impossible  to  obtain 
benzyl  mercury  compounds  directly  from  toluene.  This  may  be  due 
to  the  great  instability  of  these  compounds.  A  case  in  which  the  mer- 
curation takes  exactly  the  same  course  as  the  corresponding  bromina- 
tion is  presented  by  acetophenone  which  readily  gives  a  phenacyl 
mercuric  salt. 

The  groups  which  render  bromination  easy  have  the  same  effect 
on  mercuration.  As  a  rule,  however,  fewer  mercury  atoms  than  bro- 
mine atoms  can  be  introduced  into  a  given  compound.  Thus  aniline 
gives  o-  and  p-  and  di-mercurated  compounds.  Phenol  gives  a  similar 
result.  Just  as  nitrobenzene  is  harder  to  brominate  than  benzene  it  is 
harder  to  mercurate.  Its  reaction  with  mercuric  acetate  introduces 
us  to  an  unexplained  anomaly  of  mercuration — the  mercury  is  never 
known  to  go  in  the  meta  position  to  the  orienting  group.  Nitrobenzene 
gives  an  o-mercurated  nitrobenzene.  The  mercuration  of  benzoic  acid 
also  gives  an  ortho  compound.  The  best  method  for  making  mer- 
curated benzoic  acid  is  to  heat  ordinary  mercuric  benzoate  to  a  high 
temperature.  Benzoic  acid  is  liberated.  The  residual  mercury  com- 
pound was  long  believed  to  be  basic  mercuric  benzoate.  In  reality  it 
i«  a  C  —  Hg  compound  having  the  mercury  ortho  to  the  carboxyl 


36  COMPOUNDS  OF  MERCURY 

group.  In  this  process  the  mercuric  benzoate  plays  the  part  of  mer- 
curating  agent  and  substance  to  be  mercurated. 

C  =  0 
Heat  /  \ 

(C6H5  —  C02)  2Hg >C0H4        0  +  C6H5  —  C02H 

\/ 
Hg 

The  product  is  the  inner  salt  or  anhydride  of  o-hydroxymercuriben- 
zoic  acid.  Mercuration  experiments  have  been  performed  with  prac- 
tically all  of  the  available  substituted  anilines,  phenols,  and  aromatic 
acids.  Naphthalene  is  mercurated  in  the  alpha  position  by  mercuric 
acetate.  Anthracene  and  phenanthrene  also  give  the  reaction  but  the 
products  have  not  been  studied. 

Thiophene  reacts  easily  with  mercuric  chloride  in  the  presence  of 
sodium  acetate  giving  a-thienyl  mercuric  chloride.  Refluxing  com- 
mercial benzene  with  mercuric  acetate  yields  an  acc'-dimercurated  thio- 
phene  without  forming  more  than  a  trace  of  mercurated  benzene.  Sub- 
stituted thiophenes  are  mercurated  without  any  difficulty  if  at  least 
one  alpha  position  is  open.  If  both  alpha  positions  are  substituted 
mercuration  becomes  more  difficult.  It  is,  however,  possible  to  intro- 
duce mercury  into  one  of  the  beta  positions.  The  reaction  then  gives 
an  intermediate  compound  which  contains  the  groups  — HgX  and 
—  OH,  apparently  added  to  one  of  the  double  bonds  of  the  thiophene 
ring.  Only  long  boiling  eliminates  a  molecule  of  water  leaving  a  sub- 
stitution product  having  the  —  HgX  group  in  the  beta  position.  The 
formation  of  the  intermediate  addition  compound  in  this  case  sug- 
gests the  possibility  that  all  aromatic  compounds  are  mercurated  by 
some  such  mechanism,  the  addition  compounds  losing  water  so  readily 
that  they  cannot  be  isolated. 

A  number  of  phenyl-5-pyrazolones  have  been  mercurated  by  mer- 
curic acetate.  Three  or  four  mercury  atoms  are  introduced  into  the 
molecule.  Part  of  these  go  in  the  benzene  nucleus  and  the  rest  in 
the  pyrazolone  ring.  A  typical  example  is  the  action  of  mercuric  ace- 
tate in  cold  methyl  alcohol  on  3-methyl-l-phenyl-5-pyrazolone. 

N  —  C6H5  N  —  C6H4  —  HgOAc 

/\  /\ 

H  — N         C  =  0  H  — N          C=:0 

CH3  —  C  =  C  —  H  CH3  — C C  — HgOAc 

AcO  — Hg        OCH3 


METHODS  OF  PREPARING  MERCURY  COMPOUNDS      37 

The  resulting  product,  l-acetoxymercuriphenyl-3-methyl-3,  4-di-ace- 
toxymercuri-4-methoxy-3,  4-dihydro-5-pyrazolone,  represents  three 
different  types  of  mercuration.  The  mercury  on  the  phenyl  groups 
enters  the  same  as  in  aniline.  The  mercury  attached  to  position  4  has 
replaced  the  alpha  hydrogen  originally  there.  The  mercury  in  posi- 
tion 3  was  added  to  the  double  bond  with  the  methoxy  group  which 
is  now  attached  to  position  4.  The  study  of  other  5-pyrazolones  has 
produced  facts  of  interest  in  the  general  theory  of  substitution  in  or- 
ganic compounds.  Thus  if  no  hydrogen  is  present  in  position  4  (alpha 
to  the  carbonyl  group)  mercuration  becomes  impossible  except  at  ele- 
vated temperatures.  If  the  pyrazolone  has  a  phenyl  group  attached 
to  the  carbon  in  position  3  instead  of  to  the  nitrogen  in  position  1  it 
is  still  possible  to  mercurate  the  benzene  nucleus,  provided  there  is  a 
hydrogen  in  position  4.  This  intimate  relation  of  the  hydrogen  alpha 
to  the  carbonyl  group  in  the  pyrazolone  ring  to  the  mercuration  of  the 
benzene  nucleus  is  decidedly  interesting. 

VI.    Replacement  of  Acid  Groups  by  Mercury. 

The  last  method  of  mercuration  to  be  considered  is  the  replace- 
ment of  acid  groups  in  certain  aromatic  compounds  by  mercury.  When 
the  aromatic  boric  acids  and  sulfinic  acids  are  heated  with  mercuric 
chloride  solution  the  —  HgCl  group  takes  the  place  of  the  acid  group. 

C6H5  -  B  (OH)  2  +  HgCl2  +  H20  -*  C6H5  -  HgCl  +  HC1  +  H3B03 
C6H5  -  S02H  +  HgCl2  -*  C6H5  -  HgCl  +  SO2  +  HC1. 

A  process  very  much  like  these  two  is  the  action  of  an  aromatic  arseni- 
ous  oxide  with  mercuric  oxide.5 


2NaCl  +  2Na3AsO3  +  4H20. 

A  modification  of  these  processes  is  the  elimination  of  carbon  dioxide 
from  certain  mercuric  salts  by  heating.6  Acids  which  lose  carbon  di- 
oxide readily  yield  salts  which  have  a  similar  instability.  This  proc- 
ess is  applicable  to  both  aliphatic  and  aromatic  compounds.  It  may 
be  illustrated  by  the  general  equation, 

(R_C02)2Hg  heated  ->2C02  +  R2Hg. 

•Cliem.  Zentr.  1914  I  1469.     D.  R.  P.  272,  289. 
•Private  communication,  M.  S.  Kharasch. 


Chapter  III. 

General  Properties  and  Reactions  of  Organic  Mercury 

Compounds. 

The  important  general  reactions  of  these  substances  may  be  classi- 
fied under  the  following  headings: 

(a)  the  action  of  acids,  (b)  the  action  of  bases,  (c)  the  action  of 
sulfides,  (d)  the  change  from  compounds  of  the  type,  R  —  Hg  —  X,  to 
those  of  the  type,  R2Hg,  (e)  the  reverse  of  this  change,  that  is,  from 
R2Hg  to  R  —  Hg  —  X,  (f)  the  action  of  halogens,  (g)  the  action  of 
halides  and  cyanides  of  metals,  (h)  the  action  of  halides  of  non-metals, 
(i)  the  action  of  alkyl  and  aryl  halides,  (j)  the  action  of  acid  halides, 
and  (k)  the  action  of  metals.  In  the  next  few  paragraphs  the  general 
results  of  these  reactions  will  be  very  briefly  outlined.  Then  each  of 
the  eleven  reactions  will  be  considered  in  some  detail.  However,  the 
treatment  will  not  be  exhaustive.  Only  a  few  typical  examples  and  the 
cases  of  unusual  interest  will  be  considered  under  each  reaction.  Fur- 
ther examples  and  less  general  reactions  will  be  found  in  the  later  chap- 
ters of  the  monograph. 

The  organic  compounds  of  mercury  differ  radically  from  all  other 
compounds  having  a  metal  attached  to  carbon.  The  linkage  of  mer- 
cury to  carbon  is  capable  of  much  greater  stability  than  that  of  any 
other  metal.  Mercury  compounds  of  the  type  of  methyl  mercuric 
iodide,  CH3  —  Hg  —  I,  resemble  the  Grignard  reagent  in  formula  only. 
They  differ  from  the  magnesium  compounds  in  not  being  sensitive  to 
active  hydrogen  compounds  such  as  water,  amines,  and  alcohols.  It 
is  true  that  they  are  attacked  by  acids  giving  the  corresponding  hydro- 
carbons, but  this  action  generally  takes  place  only  with  hot  concen- 
trated halogen  acids.  Moreover  the  organomercuric  halides  give  no 
reaction  with  carbonyl  compounds.  The  organic  compounds  in  which 
both  bonds  of  the  mercury  are  attached  to  organic  residues  also  differ 
from  the  corresponding  compounds  of  other  metals  such  as  the  zinc 
alkyls,  the  mercury  compounds  being  stable  to  air  and  fairly  stable 
to  acids. 

38 


GENERAL  PROPERTIES  AND  REACTIONS      39 

The  mercury  in  most  organic  mercury  compounds  shows  none  of 
the  reactions  of  ionized  mercury.  Potassium  iodide  does  not  form 
mercuric  iodide  except  in  some  cases  in  which  it  reacts  with  an 
organomercuric  iodide  forming  a  mercury  compound  having  both 
bonds  attached  to  carbon  and  liberating  one-half  of  the  mercury  in 
inorganic  form.  This  reaction  may  be  illustrated  by  the  following 
equation, 

2R  -  Hg  - 1  +  2KI  -»  R2Hg  +  K2HgI4. 

Solutions  of  strong  bases  do  not  form  mercuric  oxide.  They  do  not, 
as  a  rule,  react  with  the  organomercuric  salts  as  these  are  salts  of 
rather  strong  bases,  the  organomercuric  hydroxides.  Thus  many  or- 
ganomercuric iodides  can  be  recrystallized  unchanged  from  hot  alkali. 
In  a  very  few  cases  compounds  of  the  type  R  —  Hg  —  R  react  with 
solutions  of  bases  giving  substances,  R  —  Hg  —  OH.  Such  a  splitting 
of  the  C  —  Hg  linkage  is  very  rare  indeed.1  The  action  of  sulfides  is 
the  most  sensitive  indicator  for  mercuric  ions,  because  of  the  extreme 
insolubility  of  mercuric  sulfide.  It  is  often  said  that  mercury  attached 
to  carbon  gives  no  mercuric  sulfide  when  treated  with  hydrogen  sulfide 
or  ammonium  sulfide.  In  reality,  the  formation  of  mercuric  sulfide  is 
usually  rather  slow,  but  it  should  be  remembered  that  the  stability 
of  the  C  —  Hg  linkage  varies  over  the  widest  range,  from  compounds 
which  give  mercuric  sulfide  almost  instantly,  to  those  which  do  not  give 
it  even  after  long  boiling  with  concentrated  hydrochloric  acid.  No  care- 
ful study  has  even  been  made  of  the  relation  between  the  constitution  of 
organic  mercury  compounds  and  the  ease  with  which  they  form  mer- 
curic sulfide.  In  cases  in  which  mercuric  sulfide  is  not  formed  im- 
mediately, an  organomercuric  sulfide  is  formed.  This,  on  standing  or 
heating,  loses  mercuric  sulfide  leaving  an  organic  mercury  compound, 
having  both  bonds  of  mercury  attached  to  carbon.  These  reactions 
may  be  illustrated  by  the  following  equations, 

2R-Hg-X  +  H2S-*  (R-Hg-)2S  +  2HX 

(R  -  Hg  -  )  2S  heated  -»  R2Hg  +  HgS. 

The  change  from  the  organic  mercury  compounds  of  the  type 
R  —  Hg  —  X  to  the  organic  compounds,  R2Hg  is  one  of  the  important 
general  reactions  of  these  substances.  The  reagents  which  bring  about 
the  change  are  most  varied.  Besides  the  inorganic  iodides  and  sul- 
fides just  mentioned  they  are  sodium  thiosulfate,  sodium  stannite  and 

'Whitmore  and  Middleton,  J.  Am.  Chem.  8oc.  43   (1921),  622. 


40  COMPOUNDS  OF  MERCURY 

various  other  alkaline  reducing  agents,  potassium  cyanide,  potassium 
sulfocyanate  and  various  metals  such  as  sodium  and  copper.  The 
various  processes  may  be  illustrated  as  follows, 

2RHgI  +  2KI  ->  R2Hg  +  K2HgI4. 

2RHgX  +  Na2S  ->  (RHg)  2S  -»  R2Hg  +  HgS. 

2RHgX  +  2Na2S203  -*  2RHgS2O3Na  -*  R2Hg  +  Na2Hg(S203)2- 

2RHgX  +  Na2SnO2  +  H20  -»  R2Hg  +  Hg  +  2NaX  +  Na2Sn03. 

2RHgX  +  2NaOH  +  2Fe  (OH)  2  ->  R2Hg  +  Hg  +  2Fe  (OH)  3. 

2RHgCN  +  2KCN  -»  R2Hg  +  K2Hg(CN)4. 

2RHgSCN  +  2KSCN  -»  R2Hg  +  K2Hg(SCN)4. 

2RHgX  +  2Na  ->  R2Hg  +  Hg  +  2NaX. 

In  each  of  these  processes  one-half  of  the  mercury  appears  as  in- 
organic mercury  and  the  other  half  remains  in  the  compound  R2Hg. 
No  one  of  these  reagents  works  satisfactorily  with  all  kinds  of  organo- 
mercuric  salts.  The  data  on  this  reaction  in  the  literature  are  en- 
tirely unsatisfactory. 

The  reverse  of  the  above  change  is  also  an  important  reaction 
of  organic  mercury  compounds. 

R2Hg  +  HgX2->2RHgX. 

In  this  instance  there  are  practically  no  complications.  In  almost 
every  case  a  substance  of  the  type  R2Hg  will  react  quantitatively 
with  a  mercuric  halide  giving  two  molecules  of  the  compound 
R  —  Hg  —  X.  The  reaction  is  brought  about  by  mixing  the  sub- 
stances in  alcohol  and  boiling  if  necessary.  It  may  be  extended  to 
mercury  salts  of  other  monobasic  acids  but  apparently  has  never  been 
completed  with  a  mercury  salt  of  a  dibasic  acid. 

Organic  mercury  compounds  react  readily  with  halogens,  giving 
products  in  which  the  position  originally  occupied  by  mercury  is  oc- 
cupied by  the  halogen.  Compounds  of  the  type  R2Hg  give  two  re- 
actions, depending  on  the  amount  of  halogen  used.  If  only  one  mole- 
cule of  the  latter  is  used  the  products  are  R  —  X  and  R  —  Hg  —  X. 
If  an  excess  of  halogen  is  used  the  organomercuric  halide  reacts  fur- 
ther, giving  another  molecule  of  R  —  X  and  a  molecule  of  a  mer- 
curic halide.  This  reaction  is  useful  in  determining  the  structure  of 
an  organic  mercury  compound  by  changing  it  to  a  known  halogen 
compound. 

The  only  reaction  in  which  the  organic  compounds  of  mercury  re- 
semble those  of  magnesium  and  zinc  is  their  action  with  the  halides 
of  various  non-metals  such  as  boron,  phosphorus,  and  arsenic.  The 


GENERAL  PROPERTIES  AND  REACTIONS  41 

reaction  with  these  substances  results  in  the  formation  of  an  organo- 
mercuric  halide  or  an  inorganic  mercuric  halide  and  a  substance  con- 
taining the  organic  residue  in  place  of  one  or  more  of  the  halogen 
atoms  of  the  halide.  Thus  phosphorus  trichloride  and  mercury  di- 
phenyl  easily  give  phenyl  mercuric  chloride  and  phenyl  dichlorophos- 
phine.  A  related  set  of  reactions  in  which  the  mercury  compounds 
fail  to  give  the  expected  products  is  that  involving  organic  halides. 
Organic  mercury  compounds  very  seldom  react  with  alkyl  halides  or 
acyl  halides  to  give  the  hydrocarbons  or  ketones  which  would  be  formed 
from  the  same  halides  by  means  of  a  Grignard  reagent  or  a  zinc  alkyl. 
The  organomercuric  halides  give  double  decomposition  reactions 
much  like  those  of  inorganic  halides.  Thus  they  act  with  silver  salts 
and  silver  oxide,  giving  the  corresponding  organomercuric  salts  and 
hydroxides.2  Phenyl  mercuric  halides  have  been  treated  with  the  ace- 
tate, nitrate,  carbonate,  and  oxide  of  silver.  The  organomercuric 
halides  do  not  react  with  sodium  derivatives  such  as  those  of  malonic 
ester  and  acetoacetic  ester. 

I.    Reaction  with  Acids. 

The  linkage  between  carbon  and  mercury  is  usually  fairly  stable 
to  dilute  acids.  Of  the  two  possible  types  of  compounds,  those  with 
both  valences  of  mercury  attached  to  carbon  are  more  easily  attacked 
by  acids.  Compounds  of  this  type  are  easily  split  by  both  inorganic 
and  organic  acids,  giving  a  hydrocarbon  and  an  organomercuric  salt. 

(CH3)2Hg  +  HC1  *  CH3HgCl  +  CH4. 

Compounds  having  only  one  bond  of  the  mercury  attached  to  car- 
bon react  less  readily  with  acids.  Inorganic  acids  at  high  tempera- 
ture will  usually  split  these  compounds  but  organic  acids  give  little 
or  no  action  unless  heated  to  a  high  temperature  under  pressure.  The 
action  of  an  inorganic  acid  may  be  illustrated  by  the  equation, 

CH3HgCl  +  HC1  ->  CH4  +  HgCl2. 

The  stability  of  the  carbon  mercury  linkage  varies  over  the  widest 
range.  Thus  substances  having  mercury  alpha  to  a  ketone  group  may 
lose  the  mercury  on  treatment  with  cold  .25  normal  hydrochloric  acid 
while  other  substances,  such  as  some  of  the  mercarbides,  are  un- 
changed even  after  long  heating  with  fuming  hydrochloric  acid.  Al- 

aOtto,  J.  pralet.  Chem.  (2)  1  (1870),  180.  Ann.  147  (1869),  164.  Cahours,  J. 
prakt.  Chem.  (2)  8  (1873),  398.  Comp.  rend.  77  (1873),  1403. 


42  COMPOUNDS  OF  MERCURY 

though  almost  all  organic  mercury  compounds  have  been  tested  for 
their  action  with  acids,  the  examples  taken  up  in  the  following  para- 
graphs will  deal  only  with  extreme  cases  or  those  of  special  interest. 

Mercury  diethyl  heated  in  a  sealed  tube  with  glacial  acetic  acid 
at  190°  gives  an  amount  of  ethane  corresponding  to  one  ethyl  group. 
A  small  amount  of  ethylene  is  formed.  Ninety-two  per  cent,  of  the 
mercury  in  the  substance  is  recovered  as  metallic  mercury.  The  other 
product  is  ethyl  acetate  which  is  obtained  in  a  yield  corresponding  to 
36%  of  the  amount  to  be  expected  if  all  of  the  second  ethyl  group  were 
changed  to  ethyl  alcohol.3  The  reaction  probably  takes  place  in  the 
following  steps. 

(C2H5)  2Hg  +  HOAc  -»  C2H6  +  C,H5  -  Hg  -  OAc. 
C2H5  -  Hg  -  OAc  -»  Hg  +  C2H5  -  OAc. 

The  last  step  is  a  thermal  decomposition  which  involves  an  intra- 
molecular oxidation  and  reduction.  In  terms  of  the  electronic  con- 
ception of  valence  this  would  mean  that  at  the  moment  of  decom- 
position the  mercury  in  the  methylmercuric  acetate  no  longer  has 

two  positive  charges  but  has  one  positive  and  one  negative  charge, 

+  _ 

thus,  Hg.  Such  a  molecule  would  be  likely  to  lose  free  mercury 
readily,  leaving  the  ethyl  and  acetate  groups  to  combine  with  each 
other.  Similar  results  have  been  obtained  with  mercury  di-isoamyl 
and  mercury  dibenzyl.4 

lodomethylmercuric  iodide,  ICH2  —  Hgl,  when  heated  with  hydro- 
chloric acid  gives  methyl  mercuric  iodide.5  If  this  observation  is  not 
due  to  some  error  it  represents  a  most  unusual  replacement  of  an 
iodine  atom  by  hydrogen. 

The  product  from  the  action  of  acetylene  with  mercuric  chloride 
(trichloromercuriacetaldehyde?)  reacts  with  cold  dilute  hydrochloric 
acid  forming  acetaldehyde,  mercuric  chloride,  and  a  trace  of  mer- 
curous  chloride.6 

As  has  been  mentioned,  the  C  —  Hg  linkage  in  the  mercarbides  is 
unusually  stable  to  acids.  Ethane  hexamercarbide,  C2Hg602(OH)2, 
reacts  with  cold  10%  hydrochloric  acid,  forming  the  salt  C2Hg,.02Cl2. 
When  this  is  heated  for  a  long  time  with  concentrated  hydrochloric 

•Jones  and  Werner,  J.  Am.  Chem.  Soc.  40   (1918),  1270. 

4J.  Am.  Chem.  Soc.  40  (1918),  1270. 

•Sakurai,  J.  Chem.  Soc.  39   (1881),  489. 

•Hofmann,  Ber.  37  (1904),  4460.     Brame,  J.  Chem.  Soc.  87  (1905),  430. 


GENERAL  PROPERTIES  AND  REACTIONS  43 

acid  it  gives  CoHg0ClG.     This  substance  is  not  changed  by  several 
days'  boiling  with  concentrated  hydrochloric  acid.7 

Another  product  obtained  from  ethane  hexamercarbide  is  the  com- 
plex  cyanide,    (CN)  —  Hg  —  C  —  C  —  Hg—  (CN).      Treatment    of 


in, 


this  substance  with  10%  hydrochloric  acid  gives  hydrocyanic  acid  but 
no  inorganic  mercury.  The  product  is  a  white  powder  having  the 
formula  (ClHg)2CH  — CH(HgCl)2.  When  this  compound  is  boiled 
with  concentrated  hydrochloric  acid  one-half  of  the  mercury  is  changed 
to  mercuric  chloride  and  the  rest  remains  in  a  volatile  compound, 
ClHg  —  CH2  —  CH2  —  HgCL  The  stability  of  this  last  compound  to 
acid  is  shown  by  the  fact  that  it  can  be  distilled  unchanged  with  concen- 
trated hydrochloric  acid.8 

Mercury  diphenyl  reacts  with  dry  hydrogen  chloride  gas,  with 
evolution  of  heat,  giving  benzene  and  mercuric  chloride.  Moderate 
treatment  with  concentrated  hydrochloric  acid  gives  phenyl  mercuric 
chloride.  Nitric  acid  even  at  — 15°  acts  violently  with  mercury  di- 
phenyl, giving  mercuric  nitrate  and  nitrobenzene.9 

Mercury  diphenyl  dissolves  easily  in  hot  organic  acids.  When  the 
mixture  is  diluted  with  water  an  organomercuric  salt  is  precipitated. 
This  is  the  method  for  making  the  formate,  acetate  and  higher  organic 
salts.10 

Mercury  diphenyl  reacts  with  N-bromoacetamide  forming  phenyl 
mercuric  bromide,  benzene,  and  methyl  isocyanate. .  The  reaction  thus 
consists  in  the  action  of  mercury  diphenyl  on  the  hydrobromic  acid 
split  from  the  bromoamide.11 

The  three  isomeric  nitrophenylmercuric  chlorides  react  with  boiling 
hydrochloric  acid  giving  nitrobenzene  and  mercuric  chloride.  The 
ortho  and  para  compounds  give  this  reaction  more  readily  than  the 
meta  compound.12 

Mercury  bis-diphenyl,  (C6H5 — C6H4 — )2Hg,  is  not  changed  even 
by  long  boiling  with  concentrated  hydrochloric  acid.13 

The  phenol  and  naphthol  mercuric  salts  are  unusually  sensitive  to 

»Hofmann,  B&r.  31   (1898),  1905;  33   (1900),  1336. 

8Hofmann,  Ber.  33   (1900),  1338. 

•Dreher  and  Otto,  Ber.  2   (1869),  543.     Ann.  154   (1870),  97  ff. 

10  Otto,  «/.  prakt.  Chem.  (2)   1  (1870),  185.     Cf.  Ann.  147  (1870),  164. 

"Kharasch,  J.  Am.  Ctiem.  Soc.  43   (1921),  May  ?. 

iaKharasch  and  Chalkley,  J.  Am.  Chem.  Soc.  43  (1921),  612. 

18Michaelis,  Ber.  28    (1895),  592. 


44  COMPOUNDS  OF  MERCURY 

dilute  mineral  acids.  The  activity  of  the  mercury  in  these  compounds 
is  almost  as  great  as  that  of  mercury  in  the  alpha  position  to  a  carbonyl 
group.14 

Phenacyl  mercuric  chloride,  C6H5  —  CO  —  CH2  —  HgCl,  is  decom- 
posed readily  by  warm  dilute  hydrochloric  acid.15 

The  compounds  obtained  from  the  nitrotoluenes  and  mercuric  oxide 
give  interesting  results  with  acids.  These  substances  have  two  mercury 

Hg  HgCl 

/      \  / 

groups  in  the  side  chain,  CH  0,  —  CH  etc. 

\      /  \ 

Hg  HgCl 

The  compound  from  o-nitrotoluene  reacts  with  cold  concentrated  hy- 
drochloric acid  giving  anthranil  which  will  react  with  sodium  hydroxide 
giving  the  sodium  salt  of  anthranilic  acid.  This  series  of  changes  from 
o-nitrotoluene  to  anthranilic  acid  represents  an  interesting  intramolec- 
ular oxidation  and  reduction.16 


\/ 

These  mercurated  nitrotoluenes  give  a  good  illustration  of  the  different 
splitting  effects  of  halogen  acids  and  oxygen  acids  on  the  C  —  Hg  link- 
age. 10  to  20  per  cent  sulfuric  acid  acts  on  the  complex  oxides  giving 

Hg 
/      \ 

stable  sulfates  containing  the  grouping,  — CH  S04.     Halogen 

\       / 

Hg 
acids  remove  the  mercury  entirely.16a 

The  mercury  compound  obtained  from  2,  4-dinitrotoluene  reacts 

"Dimroth,  Ber.  31  (1898),  2155.     Bamberger,  Ber.  31   (1898),  2G25. 
"Dimroth,  Ber.  35  (1902),  2870. 
"Reissert,  Ber.  40  (1907),  4222. 
4218. 


GENERAL  PROPERTIES  AND  REACTIONS  45 

with  nitric  acid  of  sp.  gr.  1.4  forming  2,  4-dinitrobenzoic  acid.  This 
seems  remarkable  when  it  is  recalled  that  dinitrotoluene  must  be  heated 
for  days  at  100°  with  fuming  nitric  acid  to  change  it  to  the  dinitro- 
benzoic  acid.16b 

Tetrachloromercuri  diphenylamine,  NH[C0H3(HgCl)2]2,  reacts 
with  a  mixture  of  fairly  concentrated  nitric  acid  and  sulfuric  acid  to 
form  a  substance  having  two  nitro  groups  but  only  three  — HgCl 
groups.  The  position  of  these  groups  has  not  been  determined.17 

Thiophene  mercuric  chloride  reacts  readily  with  hydrochloric  acid, 
giving  thiophene  and  mercuric  chloride.18 

The  iodomercuri  compound  of  camphor  (C10H140)3Hg4I2,  reacts 
with  halogen  acids  or  hydrochloric  acid  giving  mercuric  salts  and 
camphor.  Dilute  oxygen  acids  give  no  action.  Concentrated  nitric 
acid  gives  camphoric  acid. 

In  mercurated  5-pyrazolones  only  the  mercury  in  the  4  position 
(alpha  to  the  carbonyl  group)  is  easily  removed  by  dilute  hydro- 
chloric acid.  Thus  l-(diacetoxymercuriphenyl)-2,  3,  dimethyl-3,  4 
diacetoxymercuri-4-methoxy-3,  4-dihydro-5-pyrazolone  when  shaken 
for  12  hours  with  cold  .25  normal  hydrochloric  acid,  loses  only  the 
mercury  in  position  4,  the  other  three  mercury  atoms  remaining  in 
the  molecule.  Similar  results  are  given  by  other  5-pyrazolones.19 

One  compound  having  mercury  in  the  alpha  position  is  reported 
to  be  rather  stable  to  acids.  Bromomercuri  acetic  acid,  BrHg  —  CH2 
—  C02H,  is  not  decomposed  by  20%  nitric  acid  or  dilute  hydrochloric 
acid.20 

The  most  remarkable  reaction  of  acids  with  organic  mercury  com- 
pounds is  the  action  with  the  "addition  compounds"  obtained  from 
unsaturated  compounds  and  mercuric  salts.  These  substances  may  be 
divided  into  three  classes  which  will  be  illustrated  by  the  products  ob- 
tainable from  ethylene.  Ethylene  reacting  with  mercuric  salts  in  water 
solution  gives  two  types  of  compounds,  XHg  —  CH2.CH2OH  and 
XHg  —  CH2.CH2.O.CH2.CH2  —  HgX.  These  may  be  referred  to  as 
the  alcohol  and  ether  derivatives  respectively.  If  the  reaction  is  car- 
ried out  in  alcohol  solution  an  alkoxyl  group  is  added  instead  of  the 
hydroxyl  in  the  first  type  of  compound.  Thus  a  methyl  alcohol  solu- 

16b/6id.  4215. 

"Kharasch  and  Piccard,  J.  Am.   Chem.  Soc.   42    (1920),  1863. 
"Volhard,  Ann.  267   (1892),  174. 

19Schrauth  and  Bauerschmidt,  Bcr.  47    (1914),  2740. 
and  Sand,  Ber.  33  (1900),  1346. 


46  COMPOUNDS  OF  MERCURY 

tion  gives  XHg  —  CH2.CH2.O.CH3  which  may  be  referred  to  as  a 
mixed  ether  derivative.  The  products  to  be  expected:  from  the  action 
of  acid  on  these  substances  would  be  ethyl  alcohol,  diethyl  ether,  and 
methyl  ethyl  ether.  Such  products  are  not  obtained.  The  sole  product 
of  the  action  of  hydrochloric  acid  on  all  three  is  ethylene.  In  general 
when  an  ethylene  compound  reacts  with  mercury  salts  the  product  will 
react  with  halogen  acids  giving  back  the  original  unsaturated  com- 
pound. Corresponding  results  have  been  obtained  with  the  higher 
olefines,  with  carbon  monoxide,  with  allyl  alcohol  and  with  unsat- 
urated acids  and  their  esters,  with  terpineol,  and  with  various  allyl 
phenol  derivatives.  If  the  mercurated  products  really  have  the 
structures  indicated,  it  appears  that  oxygen  in  the  grouping  —  0  —  C 
— C  —  Hg  —  must  have  a  peculiar  reactivity  towards  acids,  or  that 
the  change  of  alcohols  and  ethers  to  olefines  is  possible  by  the  action 
of  acids  in  presence  of  mercury  salts.  Neither  of  these  possibilities 
has  received  any  experimental  study.  This  peculiar  reaction  naturally 
lead  some  chemists  to  discard  the  structural  formulas  and  assume  cer- 
tain molecular  formulas  such  as  C2H4.Hg(OH)X.  As  has  been  already 
stated,  this  type  of  formula  would  explain  the  action  of  acids  but  it 
would  not  explain  many  of  the  other  reactions  of  these  compounds. 
Thus  it  is  possible  to  change  the  "alcohol"  compounds  into  ethyl 
alcohol  by  sulfides  and  into  iodohydrine  by  iodine.  The  "ether"  com- 
pound reacts  with  iodine  giving  the  corresponding  di-iododiethyl  ether. 
The  cinnamic  ester  compound  obtained  by  the  action  of  a  methyl 
alcohol  solution  of  mercuric  acetate  reacts  with  ammonium  sulfide 
giving  methoxy  hydrocinnamic  ester. 

C6H5  —  CH  =  CH  —  C02R  -     ->  C6H5  —  CH  —  CH  —  C02R  - 

OCH3  HgOAc 
C6H5    -CH  — CH2  — C02R 

OCH3 

If  the  mercury  product  is  regarded  as  a  "molecular"  compound 
without  any  structural  relations  between  the  added  group  and  the  un- 
saturated carbons,  then  it  must  be  assumed  that  the  action  of  the 
sulfide  causes  a  molecule  of  methyl  alcohol  to  add  to  the  double  bond 
of  the  cinnamic  ester. 

The  reaction  of  acids  with  the  mercury  compounds  of  acetylene 
can  hardly  be  understood  until  the  true  nature  of  these  mercury  com- 


GENERAL  PROPERTIES  AND  REACTIONS  47 

pounds  is  settled.  As  has  been  stated,  the  treatment  with  acids  in 
most  cases  gives  a  hydration  product  of  the  original  acetylene.  In 
some  cases,  however,  this  product  is  accompanied  by  some  of  the 
original  acetylene.  Such  is  the  case  with  the  mercury  compound  of 
phenyl  acetylene.21 

The  reaction  product  of  dihydronaphthalene  and  mercuric  acetate, 
which  has  —  HgX  and  —  OH  added  to  the  2, 3  carbon  atoms,  reacts 
with  cold  30%  hydrochloric  acid  giving  pure  dihydronaphthalene.22 

A  remarkably  stable  compound  of  the  "ether"  type  is  the  product 
of  the  action  of  potassium  iodide  on  the  anhydride  of  a-hydroxymercuri 
(3-methoxy  hydrocinnamic  acid.  This  product  is  formulated  as 

C6H5  —  CH  —  CH  —  C02H 
O         Hg 

C6H5  —  CH  —  CH  —  C02H 

It  gives  no  mercuric  ions  except  on  long  boiling  with  concentrated 
nitric  or  hydrochloric  acids.23 

II.    Reaction  with  Bases. 

Bases  as  a  general  rule  do  not  break  the  carbon  mercury  linkage. 
No  case  is  known  in  which  a  true  organic  mercury  compound  gives 
mercuric  oxide  when  treated  with  a  base.  The  one  case  in  which 
alkali  breaks  the  linkage  C  —  Hg  is  that  of  the  mercurated  phenols. 
An  acetylated  mercury  diphenol,  ( AcO  —  C6H4  — )  2Hg,  when  saponi- 
fied by  sodium  hydroxide  does  not  give  the  expected  mercury  diphenol, 
(HO  —  C6H4 — )2Hg,  but  instead  gives  a  compound  having  only  one 
bond  of  the  mercury  attached  to  a  benzene  nucleus  and  the  other  at- 
tached to  oxygen.24 

Many  organic  mercury  compounds  dissolve  in  solutions  of  bases 
and  can  be  recovered  unchanged  by  cooling  or  by  cautious  treatment 
with  acid.  Thus  the  mercurated  anilines  are  soluble  in. ammonium 
hydroxide  and  can  be  recovered  by  treatment  with  acetic  acid.  In 
this  case  the  solubility  is  probably  due  to  the  formation  of  a  com- 

aManchot  and  Haas,  Ann.  399  (1913),  138. 

23  Sand  and  Genssler,  Ber.  36   (1903),  3699. 

^Schoeller,  Schrauth,  and  Struensee,  Ber.  44  (1911),  1057. 

MWhitrnore  and  Middleton,  J.  Am.  Chem.  Soc.  43  (1921),  622.  A  similar  reaction 
has  been  noted  with  5-M"ercury-bis-3-nitro-4-hydroxyphenyl  arsonic  acid  which  changes 
to  a  compound  having  only  one  organic  residue  attached  to  mercury  on  standing  with 
alkali.  Stieglitz,  Kharasch,  and  Hanke,  J.  Am.  Cliem.  Soc.  43  (1921),  May  ?. 


48  COMPOUNDS  OF  MERCURY 

pound  between  the  ammonia  and  the  mercurated  amine.     Other  in- 
organic bases  do  not  give  the  same  results.25 

Almost  all  of  the  compounds  formed  from  unsaturated  substances 
and  mercuric  salts  are  soluble  in  sodium  hydroxide  solution.  The 
acetates,  chlorides  and  bromides  are  usually  soluble  cold  and  can  be 
recovered  only  by  careful  acidification  or  better  by  saturating  the 
basic  solution  with  carbon  dioxide.  The  iodides  are  usually  soluble 
only  on  heating  and  crystallize  out  on  cooling.26  The  "ether"  com- 
pounds are  usually  less  soluble  in  bases  than  the  "alcohol"  compounds. 
This  fact  may  be  illustrated  by  means  of  the  two  compounds  obtained 
by  adding  —  HgX  and  —  OH  to  dimethylheptenol.  The  "ether"  com- 
pound, 

(CH3)2C  — CH  — Hgl 

O      CH2 

(CH3)2C-CH2, 

is    completely    insoluble    in    concentrated    KOH,    while    the    "alco- 
hol" compound 

(CH3)2C(OH)— CH  — Hgl 


A 

,4, 


H2 


(CH3)2C(OH)-CH2 

is  soluble.  Similar  relations  hold  with  cineol  mercuric  iodide  and  trans- 
terpinol  mercuric  iodide  obtained  by  addition  to  the  double  bond  of 
terpineol.27 

The  compounds  which  have  both  bonds  of  mercury  attached  to  car- 
bon are  usually  not  soluble  in  bases.  Thus,  although  the  compound, 
0(CH2  —  CH2  —  HgBr)2,  is  readily  soluble  in  bases,  the  correspond- 

CH2  — CH2 
/  \ 

ing  compound,  O  Hg,  obtained  from  it  by  alkaline  so- 

\  / 

CH2  — CH2 

dium  stannite  solution,  is  entirely  insoluble  in  sodium  hydroxide.28 

» Vecchiotti,  Gazz.  cMm.  ital.  48  II   (1918),  80.     Chem.  Abst.  13   (1919),  1450. 
2«Hofmann  and  Sand,  Ber.  33   (1900),  2694.     Sand,  Her.  34    (1901),  1391.     Sand 
and  Genssler,  Ber.  36  (1903),  3705. 

"Sand  and  Singer,  Ber.  35   (1902),  3174. 
28  Sand,  Ber.  34  (1901),  2913. 


GENERAL  PROPERTIES  AND  REACTIONS  49 

Mercury  compounds  containing  free  phenol  or  carboxyl  groups  are, 
of  course,  soluble  in  bases.  Many  mercury  compounds  of  these  two 
types  readily  form  anhydrides  or  inner  salts  which  are  insoluble  in 
water.  These  anhydro  compounds  readily  dissolve  in  alkalies,  giving 
solutions  of  the  corresponding  salts.  These  changes  may  be  illustrated 
by  the  following: 

OH  /O  ONa 

-Hg  ,/S-HgOH 


0  0 

/  / 

CH,— CH— C  CH,— CH— C—  ONa 


Hg  —  0  HgOH 

Insoluble.  Soluble. 


The  compounds  of  the  nitrotoluenes  having  mercury  in  the  side 
chain  are  stable  to  dilute  alkalies  but  react  on  long  boiling  with  con- 
centrated alkalies  giving  dark  decomposition  products,  which  have  not 
been  studied. 

An  unusually  interesting  reaction  of  bases  with  organic  mercury 
compounds  is  the  action  of  sodium  hydroxide  on  the  product  of  carbon 
monoxide  and  a  methyl  alcohol  solution  of  mercuric  acetate.  This 
substance  is  formulated  as  acetoxymercuri  formic  methyl  ester, 
AcO  —  Hg  —  C02CH3.  It  dissolves  in  sodium  hydroxide  giving  a  clear 
solution  which  gradually  deposits  metallic  mercury.  The  solution  is 
then  found  to  contain  a  carbonate.  Apparently  the  molecule 
HO  —  Hg  —  C02Na  is  very  unstable  and  readily  undergoes  intra- 
molecular oxidation  and  reduction  giving  mercury  and  sodium  bicar- 
bonate.29 

A  similar  result  is  obtained  on  the  addition  of  bases  to  iodomethyl- 
mercuric  iodide.  Metallic  mercury  is  formed  at  once.  If  the  iodide  is 
treated  with  a  suspension  of  silver  oxide,  a  water  solution  is  obtained 
which  deposits  metallic  mercury  on  standing.30 

»Schoeller  and  Schrauth,  Ber.  46  (1913),  2871. 
»°Whitmore  and  Middleton,  unpublished  results. 


50  COMPOUNDS  OF  MERCURY 

This  case  resembles  that  of  the  formate  in  that  the  unstable  product 
contains  mercury  attached  to  a  carbon  bearing  a  hydroxyl  group.  Ap- 
parently such  a  grouping  is  very  unstable. 

III.    Reaction  with  Sulfides. 

As  has  been  indicated  the  stability  of  organic  mercury  compounds 
to  sulfides  varies  over  wide  limits.  If  mercuric  sulfide  is  not  formed 
at  once  an  organomercuric  sulfide  is  obtained  which  decomposes  more 
or  less  readily  giving  mercuric  sulfide. 

RHgX-    _»(RHg)2S-     _>R2Hg  +  HgS. 

The  compounds  which  give  mercuric  sulfide  quite  rapidly  are  those 
which  have  mercury  in  the  alpha  position  to  some  group,  like  the 
carbonyl  or  phenyl,  which  renders  an  alpha  halogen  atom  unusually 
reactive.  Thus  the  bromine  in  bromoacetophenone  is  unusually  re- 
active and  the  mercury  in  the  same  position  is  very  readily  removed 
by  sulfides.  Among  the  compounds  which  react  almost  instantly  with 
sulfides  are  the  following: — 

(a)  Allyl  mercuric  iodide,  CH2  =  CH  —  CH2  —  Hgl.31 

(b)  Sodium  salt  of  hydroxymercuriacetic  acid, 

HO  — Hg  — CH2C02Na.32 

(c)  Anhydro  hydroxymercuripropionic  acid,  CH3  —  CH  —  C  =  O.33 

Hg  — 0 

In  marked  contrast  to  this  action  of  the  alpha  mercury  compound 
is  that  of  the  corresponding  beta  mercurated  compound  which  does  not 
react  with  ammonium  sulfide.3* 

(d)  Mercury  malonic   ester,35    (R02C)2CH  —  Hg  —  CH(C02R)2. 

(e)  Hydroxymercury  methyl  malonic  ester,36 

HO-Hg-C(CH3)(C02R)2. 

(f)  Hydroxymercuricyanacetic  acid  and  its  homologs.37 

»Llnnemann,  Ann.  Spl.  3  (1865),  262. 
"Schoeller  and  Schrauth,  Ber.  41  (1908),  2091. 
"Schoeller  and  Schrauth,  Ber.  42  (1909),  783. 

M76id.     Schoeller,  Schrauth,  and  Mtiller,  Biochem.  Z.  33  (1911),  401. 
wBiilmann,  Ber.  35   (1902),  2582.     Schoeller  and  Schrauth,  Ber.  41   (1908),  2091. 
Schoeller,  Schrauth,  and  Miiller,  loc.  cit.  400. 
36  Schoeller  and  Schrauth,  loc.  cit.  782. 
"Petterson,  J.  prakt.  Chem.  (2)  86  (1912),  463. 


GENERAL  PROPERTIES  AND  REACTIONS  51 


CN 

in- 

CCXH 


HgOH 


Hg-0 

(g)  Anhydro  hydroxymercurinitroacetic  ester.38       C  =  N  =  0 


2R 

(h)  Mercuribis-diazoacetic  ester.39  R02C  —  C  —  Hg  —  C  —  CO,R. 

/    \         X    \ 

(i)  "Tri-mercury  diacetone  hydrate."  40 

HgCl 

( j )  Chloromercuri  nitro  ethane.41    CH3  —  CH 

\ 

N02 

(k)  Phenacyl  mercuric  chloride.42    C6H5  —  CO  -^  CH2  —  HgCl. 
(1)  Mercurated  nitrotoluenes  containing  the  grouping 

Hg 

/      \ 
—  CH  0." 

Hg 

(m)  Mercurated  5-pyrazolones  which  have  mercury  in  the  4  po- 
sition, that  is,  alpha  to  the  carbonyl  group,  have  this  mercury  re- 
placed by  hydrogen  when  treated  with  ammonium  sulfide.  Mercury 
in  other  positions  does  not  react  readily  with  sulfides.44 

As  has  been  stated,  organic  mercury  compounds  often  react  with 
sulfides  giving  organomercuric  sulfides  of  the  type  (R  —  Hg)2S  which 
change  more  or  less  readily  to  HgS  and  R2Hg  or  to  RH  and  HgS  in 
presence  of  an  excess  of  the  sulfide.  Among  the  substances  which  be- 
have in  this  way  are  the  following: 

»Scholl  and  Nyberg,  Ber.  39   (1906),  1957. 

»Buchner,  Ber.  28  (1895),  218. 

*>Auld  and  Hantzsch,  Ber.  38  (1905),  2683 

41  Sch&ll  and  Nyberg,  loc.  cit.  1958. 

"Diraroth,  Ber.  35  (1902),  2870. 

«Reissert,  Ber.  40  (1907),  4211  ff. 

"Schrauth  and  Bauerschmidt,  Ber.  47   (1914),  2740. 


52  COMPOUNDS  OF  MERCURY 

(a)  Methyl  mercuric  salts.45    The  stability  of  the  organic  sulfide 
is  shown  by  the  fact  that  it  can  be  made  from  a  solution  of  methyl 
mercuric  chloride  in  10%  hydrochloric  acid. 

(b)  Ethyl  mercuric  chloride  reacts  with  ammonium  sulfide  giving 
a  yellowish  precipitate  of   (EtHg)2S.     This  precipitate  is  soluble  in 
an  excess  of  ammonium  sulfide.    Heating  changes  it  to  mercuric  sul- 
fide.46 

(c)  n-Hexyl  mercuric  bromide  dissolved  in  pyridine  reacts  with 
hydrogen  sulfide  at  — 10°  giving  a  white  precipitate  which  is  stable 
if  kept  dry  and  dark.     If  exposed  to  moisture  it  blackens  in  a  few 
hours.47 

(d)  Pentamethylene  di-mercuric  bromide  reacts  with  hydrogen  sul- 
fide in  pyridine  giving  a  rather  stable  sulfide.    When  the  sulfide  is  dry 
it  must  be  heated  to  160°  to  change  it  to  mercuric  sulfide.     When 
suspended  in  aniline  or  pyridine  it  blackens  at  70°.     However,  the 
change  to  mercuric  sulfide  is  not  complete,  even  after  heating  the  sus- 
pension at  175°  for  several  days.48 

Among  the  substances  of  greatest  stability  to  sulfides  are  the  mer- 
carbides.  This  undoubtedly  is  partly  due  to  their  extreme  insolubility. 
Ethane  hexamercarbide  is  only  partly  decomposed  even  after  boiling 
with  hydrochloric  acid  and  hydrogen  sulfide  for  several  days.49  A 
white  complex  sulfide  forms  readily  even  at  room  temperature.  The 
remarkable  stability  of  the  C  —  Hg  linkages  in  this  sulfide  may  be 
seen  from  the  fact  that  treatment  of  the  compound  with  chlorine  wa- 
ter, nitric  acid,  and  then  with  sodium  hydroxide  gives  back  the  origi- 
nal mercarbide.50  Treatment  of  the  mercarbide  with  potassium  poly- 
sulfide  and  then  with  hydrochloric  acid  gives  a  compound, 

ClHg  — CH CH  — HgCl.51 

Hg— S-Hg 

The  mercarbide,  Hg  =  C C  =  Hg,  obtained  from  the  hexamercar- 

CN  — Hg       Hg  — CN 

«Frankland,  Ann.  85  (1853),  363.     Otto,  Ann.  154   (1870),  199.     Hilpert  and  Dit- 
mar,  Ber.  46   (1913),  3740. 

^Diinhaupt,  J.  praJct.  Ch&m.   (1)   61    (1854),  426. 

«Griittner,  Ber.  47  (1914),  1655. 

«  Hilpert  and  Griittner,  Ber.  47   (1914),  182. 

»Hofmann,  Ber.  31   (1898),  1905. 

^Hofmann,  Ber.  33   (1900),  1337. 

"Hofmann  and  Feigel,  Ber.  38   (1905),  3«57. 


GENERAL  PROPERTIES  AND  REACTIONS      53 

bide  by  treatment  with  potassium  cyanide  reacts  with  hydrogen  sulfide 
in  cold  15%  nitric  acid  giving  the  corresponding  —  SH  compound, 
C2Hg4(SH)2.52  Ethylene  di-mercuric  chloride,  ClHg— CH2.CH2— HgCl, 
obtained  from  the  cyanide  just  mentioned,  reacts  with  hydrogen  sul- 
fide in  hydrochloric  acid  solution  giving  a  white  sulfide  which  is  in- 
soluble in  20%  cold  nitric  acid  but  can  be  recrystallized  from  hot 
alcohol. 

The  products  formed  from  ethylene  compounds  and  mercuric  salts 
react  with  siilfides  in  three  ways.  Some  give  organomercuric  sulfides 
of  greater  or  less  stability.  Others  give  the  original  unsaturated  com- 
pounds, and  still  others,  under  proper  conditions,  give  compounds  con- 
taining a  molecule  of  water  or  alcohol  added  to  the  original  double 
bond.  These  changes  may  be  illustrated  by  the  following, 

R       R    R          R        R  R        R 

CH=CH^HO— CH— CH— HgX-*  (HO— CH— CH— Hg)  2S  Complex 

sulfide. 
R        R 

CH=CH     Original  unsatu- 
rated compound. 
R        R 


HO  — CH  — CH2   "Alcohol"  com- 
pound. 
R        R 

R'O— CH— CH— HgX->  R'O— CH— CH2  "E  t  h  e  r"    com- 
pound. 

This  last  type  of  reaction  is  of  greatest  interest  as  it  throws  light 
on  the  constitution  of  the  mercury  addition  products.  The  best  way 
to  obtain  this  result  is  to  dissolve  the  mercury  compound  in  sodium 
hydroxide,  if  possible,  and  then  pass  in  hydrogen  sulfide  in  excess. 
The  mercury  sulfide  held  in  solution  by  the  alkaline  sulfide  is  precipi- 
tated by  adding  an  ammonium  salt  and  the  organic  product  is  extracted 
from  the  filtered  solution.  If  the  mercury  compound  is  not  soluble  in 
sodium  hydroxide  the  same  result  may  sometimes  be  obtained  by  dis- 
solving it  in  alcohol  and  then  passing  in  hydrogen  sulfide  and  ammonia 
gas.  The  following  compounds  have  been  found  to  give  this  re- 
action:— 

"Hofmann,  Ber.  33   (1900),  1338. 


54  COMPOUNDS  OF  MERCURY 

(a)  Anhydro   a-hydroxymercuri    (3-hydroxy butyric    acid   obtained 
from  crotonic  acid  when  treated  with  sodium  hydroxide  and  hydrogen 
sulfide  gives  p-hydroxy  butyric  acid.    If  the  reaction  is  carried  out  in 
acid  solution  crotonic  acid  is  the  product.53 

(b)  The    sodium    salt    of    hydroxymercuri    hydroxysuccinic    acid 
obtained  from  maleic  acid  reacts  with  sodium  hydroxide  and  hydrogen 
sulfide  giving  about  80%  of  the  calculated  amount  of  malic  acid.54 

(c)  The  anhydride  obtained  from  allocinnamic  acid  and  mercuric 
salts  reacts  with  sodium  hydroxide  and  hydrogen  sulfide  giving  phenyl 
hydracrylic  acid,  C0H5  —  CHOH  —  CH2  —  C02H.    If  the  reaction  is 
carried  out  in  hot  acid  solution  the  product  is  common  cinnamic  acid.55 

(d)  The  a-acetoxymercuri-p-alkoxyl  hydrocinnamic  esters  obtained 
from  cinnamic  esters  and  mercuric  acetate  in  various  alcohols  react 
with  ammonia  and  hydrogen  sulfide  forming  the  corresponding  |3-alk- 
oxyl  hydrocinnamic  esters. 

CGH5  —  CH  —  CH  —  C02R'   NH3   C6H5  —  CH  —  CH2  —  C02R' 

OR      HgX  ~H£*  OR 

The  reaction  has  been  carried  out  with  alkoxyl  derivatives  of  the  fol- 
lowing alcohols,  methyl,  ethyl,  n-propyl,  isopropyl  and  isobutyl.56 
Mercury  di-p-phenyl  anhydrohydracrylic  acid, 

C6H5  —  CH  —  CH  —  C02H 

A    L       , 

C6H5  —  CH  —  CH  —  C02H 

obtained  from  the  anhydro  methoxy  hydroxymercuri  hydrocinnamic 
acid  and  potassium  iodide  is  remarkably  stable  to  sulfides.  Its  solu- 
tion in  ammonium  hydroxide  gives  no  mercuric  sulfide  even  on  long 
boiling  with  ammonium  sulfide.  Only  after  long  boiling  with  concen- 
trated hydrochloric  acid  or  nitric  acid  will  it  give  any  action  with 
sulfides.57 

Most  of  the  other  products  obtainable  from  ethylene  compounds 
and  mercuric  salts  have  been  found  to  act  more  or  less  readily  with 
sulfides  but  little  attempt  has  been  made  to  identify  the  organic  prod- 

B3Biilmann,  Ber.  35  (1902),  2576;  43  (1910),  579. 

"IMd.  577. 

85  Ibid. 

"Schoeller,  Schrauth,  and  Struensee,  Ber.  43  (1910),  C98  ;  44   (1911),  1432. 

"Schoeller,  Schrauth,  and  Struensee,  Ber.  44   (1911),  1057. 


GENERAL  PROPERTIES  AND  REACTIONS      55 

ucts.  Ethanol  mercuric  chloride  in  alkaline  solution  reacts  with  po- 
tassium sulfide  giving  a  white  precipitate  of  (HO  —  CH2.CH2  —  Hg)2S 
which,  on  boiling  with  water,  is  hydrolyzecT  to  the  corresponding  sulf- 
hydrate  and  hydroxide,  without  giving  any  mercuric  sulfide.58  Di-ethyl 
ether  di-mercuric  bromide  in  alkaline  solution  reacts  with  potassium 
sulfide  giving  a  white  precipitate  which  is  insoluble  in  hot  potassium 
hydroxide.59 

Acetoxymercuriformic  methyl  ester  obtained  from  carbon  monoxide 
and  a  methyl  alcohol  solution  of  mercuric  acetate  reacts  with  a  small 
amount  of  hydrogen  sulfide  in  the  cold  giving  a  white  sulfide  which 
blackens  on  standing,  heating,  or  treating  with  hydrochloric  acid.60 

Some  of  the  mercury  addition  products  obtained  from  allyl  com- 
pounds such  as  safrol  and  the  methyl  ether  of  eugenol  do  not  react 
with  ammonium  sulfide  but  are  blackened  by  hydrogen  sulfide.  This 
phenomenon  has  not  been  explained.61 

The  compound,  C10H160(HgOAc)2,  obtained  from  camphene  and 
mercuric  acetate  reacts  slowly  with  hydrogen  sulfide  and  dilute  hy-; 
drochloric  acid  giving  mercuric  sulfide  and  camphene.62 

The  reaction  of  5-pyrazolones  having  mercury  in  the  4-position, 
alpha  to  the  carbonyl  group,  has  been  mentioned.  Most  of  these  mer- 
curated  pyrazolones  also  have  mercury  in  the  3  position  which  was 
put  there  by  addition  of  the  groups  —  HgOAc  and  OCH3  to  the  double 
bond  between  the  3  and  4  carbon  atoms.  This  mercury  is  not  attacked 
by  sulfides  as  readily  as  the  mercury  in  the  4  position.  Long  standing 
with  ammonium  sulfide  is  necessary  to  give  mercuric  sulfide.63 

l-phenyl-3-methyl-4-acetoxymercuri-5-chloro  pyrazoline  is  not 
blackened  immediately  by  ammonium  sulfide.64 

Mercury  acetylide  reacts  violently  with  ammonium  sulfide  giving 
mercuric  sulfide  and  acetylene.65  The  product  from  mercuric  chloride 
and  acetylene  is  blackened  at  once  by  ammonium  sulfide  but  gives 
only  1%  of  the  acetylene  used  in  its  preparation.66 

The  mercury  compounds  of  the  trihalogen  ethylenes  and  the  mono- 

"Hofmann  and  Sand,  Ber.  33  (1900),  1350. 
89  Ibid.,  2695. 

6°Schoeller  and  Schrauth,  Ber.  46  (1913),  2872. 

ttlBalbiano  and  Nardacci,  Gazz.  cMm.  ital.  36  I  (1906),  270.  Manchot,  Ann.  421 
(1920),  320. 

62Balbiano,  Ber.  36  (1903),  3577.     Gazz.  cUm.  ital.  loc.  cit. 

63  Schrauth  and  Bauerschmidt,  Ber.  47   (1914),  2740. 

M  Ibid: 

« Manchot  and  Haas,  Ann.  399   (1913),  152. 

"Blitz  and  Reinkober,  Ann.  404   (1914),  224. 


56  COMPOUNDS  OF  MERCURY 

halogen  acetylenes  react  at  once  with  ammonium  sulfide.67  The  mer- 
cury compounds  of  phenyl  acetylene  do  the  same.68 

The  aromatic  mercury  compounds  with  the  exception  of  the  mer- 
curated  phenols  are  more  stable  to  sulfides  than  the  aliphatic  com- 
pounds. Phenyl  and  tolyl  mercuric  salts  form  the  organomercuric  sul- 
fides in  the  usual  way.  This  is  one  important  method  of  changing  them 
to  mercury  diphenyl  and  mercury  ditolyl.  Long  continued  action  of 
hydrogen  sulfide  changes  all  of  the  organic  mercury  to  mercuric  sul- 
fide and  leaves  hydrocarbons,69 

Many  of  the  mercurated  anilines  react  with  barium  sulfhydrate 
solution  giving  organic  mercury  sulfides  which  on  heating  give  the 
mercury  di-anilines.  The  reaction  has  been  carried  out  with  aniline, 
methyl  aniline,  dimethyl  aniline,  ethyl  aniline,  diethyl  aniline  and 
acetanilide.70 

If  the  product  of  the  action  of  the  calculated  amount  of  barium 
sulfhydrate 71  solution  or  dilute  sodium  sulfide  solution  is  warmed  with 
50%  sodium  sulfide  the  mercury  is  entirely  eliminated  as  mercuric 
sulfide.72 

The  mercurated  phenols  do  not  give  mercuric  sulfide  at  once  on 
treatment  with  sulfides  but  the  organic  mercury  sulfides  formed  de- 
compose more  readily  than  most  aromatic  compounds  of  this  type.73 

The  mercurated  nitrophenols  do  not  give  mercuric  sulfide  with 
ammonium  sulfide  or  hydrogen  sulfide.74 

Mercury  fluorescein  dissolved  in  ammonium  hydroxide  and  heated 
with  ammonium  sulfide  gives  mercuric  sulfide.75 

A  careful  study  has  been  made  of  the  speed  with  which  ammonium 
sulfide  blackens  the  sodium  salts  of  various  mercurated  benzoic  acids 
containing  the  group  — HgOH.  The  time  in  minutes  required  for 
blackening  the  sodium  salts  is  as  follows:  salicylic  14,  anthranilic  20, 
sulfosalicylic  60,  o-toluic  145,  o-iodobenzoic  170,  o-chlorobenzoic  255, 
benzoic  540.  The  greater  stability  of  the  compounds  having  both 

67Hofmann  and  Kirmreuther,  Ber.  41  (1908),  315;  42  (1909),  4235. 

88  Manchot  and  Haas,  loc.  cit.  138  ff. 

»Dreher  and  Otto,  Ann.  154  (1870),  116,  174.  Otto,  J.  prakt.  Chem.  (2)  1  (1870), 
182.  Dreher  and  Otto,  Ber.  2  (1869),  544. 

™Pesci,  Gazz.  chim.  ital.  29  I   (1899),  394. 

7lPiccinini,  Qazz.  chim.  ital.  23  II  (1893),  537.  Pesci,  Z.  anorg.  Chem.  15  (1897), 
217  ff.  Dimroth,  Ber.  35  (1902),  2044. 

"Pesci,  &aez.  cUm.  ital.  23  II  (1893),  524. 

"Dimroth,  Chem.  Z&ntr.  1901  I  451.  Ber.  35  (1902),  2866. 

"Hantzsch  and  Auld,  Ber.  39   (1906),  1110. 

75  D.  R.  P.  308,  335.     Chem.  Alst.  13   (1919),  1621. 


GENERAL  PROPERTIES  AND  REACTIONS  57 

bonds  of  the  mercury  attached  to  aromatic  residues  is  shown  by  the 
fact  that  the  sodium  salt  of  mercury  dibenzoic  acid  is  blackened  only 
after  three  weeks  standing  with  ammonium  sulfide.  Inorganic  halide 
solutions  exert  a  profound  effect  on  the  formation  of  mercuric  sulfide 
from  these  compounds.  The  addition  of  a  5%  solution  of  ammonium 
chloride  cuts  down  the  time  required  for  blackening  from  14  minutes 
to  2  minutes  for  the  salicylic  derivative  and  from  540  to  135  for  the 
benzoic  compound.76 

The  mercurated  benzoic  acids  form  organic  mercuric  sulfides  which 
can  be  changed  to  the  mercury  dibenzoic  acids  by  heating.77  The 
corresponding  acid  chloride  (C1CO  —  C6H4  —  Hg)2S,  when  boiled  with 
methyl  alcohol  gives  o-chloromercuribenzoic  methyl  ester,  methyl  ben- 
zoate,  mercuric  sulfide,  and  hydrochloric  acid.  In  all  probability  the 
R2Hg  compound  is  formed  here  as  usual  but  is  split  into  RH  and 
R  —  Hg  —  Cl  by  the  hydrochloric  acid  formed  from  the  acid  chloride 
and  the  alcohol.78 

Similar  complex  sulfides  have  been  made  from  mercurated  amino- 
benzoic  acids  and  their  esters79  and  from  mercurated  salicylic  acid 
and  other  hydroxybenzoic  acids  and  esters.80  o-Chloromercuribenzo- 
phenone  reacts  very  slowly  with  hydrogen  sulfide  even  when  heated.81 
The  carbinol  obtained  from  the  action  of  this  mercurated  ketone  with 
ethyl  magnesium  bromide  is  even  more  stable  to  sulfides.82 

An  alcoholic  solution  of  a-mercury  dinaphthyl  does  not  act  with 
hydrogen  sulfide.83  ct-Naphthyl  mercuric  acetate  in  alcohol  reacts  with 
sulfides  giving  a  white  precipitate.  An  excess  of  ammonium  sulfide  at 
100°  converts  this  to  mercuric  sulfide  and  naphthalene.84 

Dimercurated  a-naphthylamine  reacts  very  slowly  with  ammonium 
sulfide.85  The  mercury  derivatives  of  the  sulfonic  acids  of  a-naphthyl- 
amine show  a  similar  behaviour.86 

™  Schoeller,  Schrauth,  and  Miiller,  Biochem.  Z.  33  (1911),  403. 

"Pesci,  Qazz.  chim.  ital.  32  II  (1902),  292;  CTiem.  Zentr.  1902  II  1454.  Schoeller 
and  Schrauth,  Ber.  53  (1920),  637. 

"Sachs,  Ber.  53  (1920),  1740. 

78  Blumenthal,  Biochem.  Z.  32  (1911),  60  ff.  Schoeller  and  Hueter,  Ber.  47  (1914), 
1935.  Schoeller,  Schrauth,  and  Liese,  Ber.  52  (1919),  1784. 

«°Rupp,  Arch.  Pharm.  239  (1901),  114;  Chem.  Zentr.  1901  I  972.  Dimroth,  Ber. 
35  (1902),  2872.  Schoeller,  Schrauth,  and  Milller,  Biochem.  Z.  33  (1911),  400.  Chem. 
Aost.  5  (1911),  3880.  Schoeller  and  Schrauth,  Ber.  53  (1920),  639. 

"Dimroth,  Ber.  35   (1902),  2868. 

8aGrignard  and  Abelmann,  Bull.  soc.  chim.   (4)   19   (1916),  25. 

83  Otto  and  Mories,  Ann.  147  (1868),  171. 

84  Otto,  Ann.  154   (1870),  191. 

"Brieger  and  Schulemann,  J.  prakt.  Chem.   (2)  89  (1914),  141. 

88  Ibid.  151  ff.  T 


58  COMPOUNDS  OF  MERCURY 

Monomercurated  (3-nnphthylamine  is  blackened  instantly  by  am- 
monium sulfide.87  The  sodium  salt  of  l-hydroxymercuri-|3-naphthyl- 
amine-6-sulfonic  acid  is  obtained  in  two  forms,  a  yellow  anhydride 

Hg 


apparently  containing  the  grouping, 


NH 


,  which  reacts  instantly 


giving  mercuric  sulfide,  and  a  hydrated  colorless  form  which  does  not 
act  with  ammonium  sulfide.88 

a-Naphthol  reacts  with  mercuric  acetate  giving  a  yellow  gel  which 
is  blackened  at  once  by  ammonium  sulfide.  The  corresponding  hy- 
droxide gives  no  action  until  it  has  stood  with  ammonium  sulfide  for  a 
few  minutes.  The  di-mercurated  product  from  a-naphthol  does  not  re- 
act with  ammonium  sulfide  at  all.  The  same  is  true  of  the  mer- 
curated  a-naphthol-4-sulfonic  acid.89 

Mercury  derivatives  of  (3-naphthol  and  its  sulfonic  acids  and  car- 
boxylic  acids  are  very  stable  to  ammonium  sulfide.  The  addition  of 
inorganic  halides,  especially  iodides,  hastens  the  formation  of  mer- 
curic sulfide  apparently  by  exerting  a  "loosening"  action  on  the  C  —  Hg 
linkage.90 

The  mercurated  thiophenes  in  alcohol  solution  react  with  hydrogen 
sulfide  giving  mercuric  sulfide.91 

Tyrosin  forms  a  mercury  compound  which  is  stable  to  hydrogen  sul- 
fide.92 Mercury  phenosafranine  reacts  with  hot  ammonium  sulfide 
very  slowly  giving  mercuric  sulfide.93 

The  mercury  derivatives  of  theobromine  and  theophylline  do  not 
act  with  ammonium  sulfide.94 

Various  compounds  of  mercury  salicylic  acid  are  more  stable  to  sul- 
fides  than  the  substance  itself.  Thus  the  sodium  salt  of  mercurated 
salicylic  acid  is  blackened  in  14  minutes  while  its  compound  with  so- 
dium amino-oxyisobutyrate  is  blackened  only  after  30  minutes.95 
Even  more  remarkable  substances  are  the  water  soluble  compounds 

87Brleger  and  Schulemann,  J.  prakt.  Chem.   (2)   89   (1914),  141. 
MJ6id.  145. 
88/6id.   135  ff. 

wiua.  105  ff. 

•'Volhard,  Ann.  267   (1892),  175. 

nD.  R.  P.  267,  411.     Frankel,  Die  Arxneimittelsynthese,  1919,  p.  661. 

83  Chem.  Zentr.  1915  II  569. 

94  D.  R.  P.  282,  377.     Frankel,  676. 

«Schoeller,  Schrauth,  and  Miiller,  Biochem.  Z.  33  (1911),  381. 


GENERAL  PROPERTIES  AND  REACTIONS  59 

obtained  from  mercury  salicylic  acid  and  the  mercurated  sul- 
famido  benzoic  acids.  The  latter  compounds  contain  the  group 
-  SO2  —  NH  —  HgOH  and  react  instantly  with  cold  ammonium  sul- 
fide  as  do  all  N  —  Hg  compounds.  However  their  compounds  with 
mercury  salicylic  acid  give  mercuric  sulfide  only  on  boiling  with  am- 
monium sulfide. 

Recently  the  reactivity  of  a  number  of  mercury  derivatives  of 
dihydroxy  and  amino  hydroxy  benzenes  with  sulfides  has  been 
studied.96  It  is  found  that  if  both  groups  are  "protected"  by  methyla- 
tion  or  acylation  the  substance  does  not  act  readily  with  sulfides.  Ace- 
toxymercuriresorcinol  reacts  at  once  with  ammonium  sulfide.  Diace- 
toxymercuriresorcinol  dimethyl  ether  is  very  stable  to  ammonium  sul- 
fide. Acetoxymercuricatechol  monomethyl  ether  is  fairly  stable  to  sul- 
fides. Acetoxymercuri-m-hydroxy-dimethylaniline  reacts  readily  with 
ammonium  sulfide.  The  corresponding  acetyl  derivative  is  stable  to 
ammonium  sulfide.  4,  4'-Mercuribis-(3-hydroxyphenyl-trimethyl-am- 
monium  acetate)  is  exceedingly  stable  to  ammonium  sulfide. 

IV.     Change  of  Compounds  of  the  Type  K-Hg-X  to  Those  of  the 
Type  R-Hg-R. 

In  a  few  cases  this  change  takes  place  spontaneously  or  on  heating 
without  the  addition  of  any  reagent.  It  may  be  represented  by  the 
equations 

2RHgX  =  R2Hg  +  HgX, 
(RHg)2Y"  =  R2Hg+HgY" 

in  which  X  and  Y  are  univalent  and  bivalent  acid  radicals.  The  only 
compounds  of  the  first  class  which  undergo  the  change  without  the  ad- 
dition of  any  reagent  are  the  a-thiophene  mercuric  iodides.  When  an 
attempt  is  made  to  prepare  these  compounds  in  the  usual  way  by  treat- 
ing the  chloride  with  one  molecule  of  sodium  iodide  a  considerable 
amount  of  mercury  dithienyl  crystallizes  out  and  a  correspondingly 
smaller  amount  of  the  iodide  is  obtained  from  the  mother  liquors.  To 
the  second  class  of  compounds  belong  the  organomercuric  sulfides 
and  thiosulfates  which  decompose  on  heating.  The  length  of  time  taken 
for  this  decomposition  varies  over  a  wide  range.  In  most  cases  the 
best  way  to  bring  about  the  changes  represented  in  these  equations 
if  they  will  not  take  place  on  heating  is  to  add  an  excess  of  a  substance 
which  will  remove  HgX2  or  HgY  either  by  changing  them  to  metallic 

M  Private  communication,  Kharasch  and  Cbalkley. 


60  COMPOUNDS  OF  MERCURY 

.  ^ 
3 

mercury  or  to  a  complex  mercuric  ion.  Even  in  those  cases  where 
heat  alone  will  cause  the  change  the  addition  of  some  such  reagent 
hastens  the  reaction.  Thus  the  change  from  an  organomercuric  thiosul- 
fate  to  the  R2Hg  compound  is  hastened  by  using  an  excess  of  con- 
centrated sodium  thiosulfate  which  forms  sodium  mercuric  thiosulfate, 

Na,Hg(StO.),. 

The  iodides  which  have  been  found  to  change  to  the  R2Hg  com- 
pounds on  heating  are  a-thiophene  mercuric  iodide  and  a'-iodo-a-iodo- 
mercuri  thiophene.  The  corresponding  bromo  and  chloro  compounds 
are  changed  to  R2Hg  only  by  an  excess  of  the  iodide  which  removes 
the  mercuric  iodide  as  Na2HgI4.  When  the  --  Hgl  group  is  in  the 
beta  position  the  change  to  the  R2Hg  compound  does  not  take  place 
spontaneously  or  even  in  presence  of  an  excess  of  inorganic  iodide. 
This  change  has  been  brought  about  only  by  the  action  of  metallic 
sodium  in  boiling  xylene. 

In  the  case  of  some  substituted  anilines,  the  action  of  an  excess  of 
alcoholic  sodium  or  potassium  iodide  is  the  best  way  to  make  the 
R2Hg  compound.  Such  a  case  is  that  of  o-acetoxymercuri-p-bromo- 
dimethylaniline  which  gives  an  86%  yield  of  the  mercury  diphenyl  de- 
rivative on  refluxing  for  8  hours  with  potassium  iodide.97  The  theory 
that  this  action  is  due  to  a  complex  formation  is  strengthened  by  the 
fact  that  it  is  given  only  to  a  limited  extent  by  bromides  and  not  at  all 
by  chlorides. 

The  most  remarkable  reaction  of  this  type  given  by  potassium 
iodide  is  its  reaction  with  anhydro  a-hydroxymercuri-p-methoxy  hy- 
drocinnamic  acid,  C6H5  —  CH  —  —  CH  — C  =  0,  forming  a  mercury 

OCH3     Hg  — O 

C6H5— CH— CH— C02H 

di-p-phenyl-anhydro-hydracrylic  acid, —  O        Hg  ,98 

C6H5— CH— CH— C02H 

This  interesting  substance  has  only  been  tested  for  its  action  with  sul- 
fides  and  acids  towards  both  of  which  it  is  unusually  stable. 

The  hypothesis  that  the  change  from  R  —  Hg  —  X  to  R2Hg  re- 
quires some  reagent  which  is  capable  of  removing  mercuric  ions  either 
as  metallic  mercury  or  as  some  slightly  ionized  complex  "  leads  to  ex- 

"Whitmore,  J.  Am.  Chem.  Soc.  41   (1919),  1850. 
MSchoeller,  Schrauth,  and  Struensee,  Ber.  44  (1911),  1056. 
99  Whitmore,  loc.  cit. 


GENERAL  PROPERTIES  AND  REACTIONS  61 

periments  on  the  action  of  potassium  sulfocyanate  on  compounds  of 
the  type  R  —  Hg  —  X.  The  stability  of  the  sulfocyanate  complexes 
of  mercury  would  favor  the  formation  of  the  R2Hg  compound  ac- 
cording to  the  following  equation, 

2RHgX »R2Hg  +  HgX2, 

the  mercuric  salt  being  removed  by  the  sulfocyanate  ions.  Such  ap- 
pears to  be  the  case  when  certain  mercurated  phenols  and  aromatic 
amines  are  refluxed  with  potassium  sulfocyanate  in  aqueous  alcohol. 
The  corresponding  substituted  mercuribis-phenols  and  mercuribis-ani- 
lines  are  obtained.100 

The  sodium  thiosulfate  method  is  probably  the  most  general  for 
changing  compounds  of  the  type  RHgX  to  those  of  the  type  R2Hg  in 
which  both  bonds  of  mercury  are  attached  to  carbon.  It  works  best 
with  substances  which  dissolve  readily  in  the  concentrated  solution. 
On  standing  the  R2Hg  compound  separates  leaving  the  inorganic  mer- 
cury in  the  solution.  In  some  cases  the  thiosulfate  treatment  gives  an 
intermediate  compound  which  can  be  isolated.  This  has  the  formula 
R  —  Hg  —  S  —  S03Na.  The  reaction  has  been  carried  out  with  the 
following  substances: 

(a)  Phenyl  mercuric  compounds.101 

(b)  Substituted  aniline  and  toluidine  mercury  compounds.102 

(c)  Mercury  compounds  of  diphenyl  amine  and  methyl  diphenyl 
amine.103    Tetra  chloromercuri  diphenyl  amine  gives  a  compound  which 
has  the  two  benzene  nuclei  attached  by  two  mercury  bridges.104 

(d)  Phenol  mercury  compounds.105 

(e)  Aminobenzoic  acid  mercury  compounds.106 

(f)  Salicylic  ester  mercury  compounds.107 

The  sulfide  method  for  making  R2Hg  has  already  been  discussed 
under  the  reactions  with  sulfides.  The  organomercuric  sulfide  is  usu- 
ally prepared  and  dried  and  then  heated  at  about  100°.  The  residue 
consisting  of  mercuric  sulfide  and  the  desired  product  is  extracted  with 

100  whitmore,  unpublished  results. 

101Pescl,  Gazz.  chim.  ital.  29  I  (1899),  394.     Chem.  Zentr.  1899  II  481. 

1MPesci,  Z.  anorg.  Chem.  15  (1897),  212;  17  (1898),  282.  Prussia,  Gazz.  chim. 
ital.  27  I  (1897),  17.  Dimroth,  Ber.  35  (1902),  2041. 

»•  Prussia,  Gazz.  chim.  ital.  28  II  (1898),  129.     Chem.  Zentr.  1898  II  928. 

«*Kharasch  and  Piccard,  J.  Am.  Ghem.  Soc.  42  (1920),  1861. 

10*  Dimroth,  Chem.  Zentr.  1901  I  451.  Ber.  35  (1902),  2855.  Whitmore  and  Mid- 
dleton,  J.  Am.  Chem.  Soc.  43  (1921),  622. 

108Schoeller  and  Hueter,  Ber.  47  (1914),  1936.  Schoeller  and  Schrauth,  Ber.  53 
(1920),  642. 

1OT  76i<*. 


62  COMPOUNDS  OF  MERCURY 

benzene  or  carbon  disulfide  in  which  the  former  is  insoluble.  In  the 
case  of  2-acetoxymercuri-4-nitrophenol  the  action  of  sodium  sulfide  in 
the  cold  gives  two  kinds  of  complex  sulfides.  The  first  one  formed 
has  the  usual  formula  (RHg)2S.  When  heated  it  gives  R2Hg  and  a 
more  complex  sulfide  (RHg  —  S)2Hg  which  can  be  recrystallized  from 
acetone.  On  heating  it  gives  2HgS  and  R2Hg.108  The  sulfide  reaction 
has  been  applied  in  making  mercury  dimethyl,109  mercury  diphenyl,110 
various  mercury  dianilines,111  mercury  bis-acetanilide,111  mercury  di- 
salicylic  ester,112  mercury  dibenzoic  ester,113  mercury  diphenols,114  and 
5-mercury-bis-3-nitro-4-hydroxyphenyl  arsonic  acid.115 

The  change  to  the  R2Hg  compound  can  be  brought  about  by  re- 
duction in  neutral  or  alkaline  media.  Acid  reduction  is  excluded  as  it 
removes  the  mercury  completely.  The  commonest  reducing  agent 
used  is  an  alkaline  solution  of  sodium  stannite.  It  seems  probable 
that  the  process  here  takes  the  course  which  it  does  with  inorganic 
mercury  compounds  forming  a  mercurous  compound  and  then  metallic 
mercury.  In  this  case  an  organic  "mercurous"  compound  of  the  type 
R  —  Hg  —  Hg  —  R  is  perhaps  first  formed.  It  then  decomposes  to 
metallic  mercury  and  R  —  Hg  —  R.  The  only  case  in  which  the  mer- 
curous compound  has  been  isolated  is  in  the  action  of  sodium  stannite 
on  the  ethyl  ether  compounds  obtained  from  ethylene. 

CH2  —  CH2  —  HgX  CH2  —  CH2  —  Hg 

/  Na2Sn02  / 

0  — »0 

\  \ 

CH2  — CH2  — HgX  CH2  — CH2  — Hg 

CH2  — CH2 

140°      /  \ 
>        0  Hg116 

\    .  / 

CH2  —  CH2 

If  it  is  eventually  proved  that  these  ethyl  ether  compounds  are 
really  only  molecular  compounds  the  "mercurous"  compound  will  have 

108Fourneau  and  Vila,  J.  phwm.  chim.   (7)   6   (1912),  433. 
1TOHilpert  and  Ditmar,  Ber.  46  (1913),  3740. 
"°Dreher  and  Otto,  Ann.  154  (1870),  116. 

luPesci,  Gazz.  chim.  ital.  23  II  (1893),  526.   Piccinini,  Ibid.  541.    Ruspaggiari,  Ibid. 
547.     Chem.  Zentr.  1894  I  501.     Pesci,  Z.  anorg.  Chem.  15   (1897),  217. 
«2  Scnoeller  and  Schrauth,  loc.  cit.  640. 

113 Ibid.  637.   Pesci,  G-azz.  chim.  ital.  32  II  (1902),  295.    Chem.  Zentr.  1902  II  1454. 
114  Dim  roth,   Chem.  Zentr.  1901  I  451.     Fourneau  and  Vila,  loc.  cit. 
"5Stieglitz,  Kharasch,  and  Ilanke,  J.  Am.  Chem.  Soc.  43  (1921),  May  ? 
118  Sand,  Ber.  34  (1901),  2913. 


GENERAL  PROPERTIES  AND  REACTIONS  63 

to  be  regarded  as  an  addition  product  of  ethylene  and  mercurous  oxide 
and  the  final  product  as  one  of  ethylene  and  mercuric  oxide. 

In  a  few  other  cases  a  temporary  purple  or  red  color  followed  by 
the  gray  of  metallic  mercury  may  indicate  the  formation  of  a  very  un- 
stable mercurous  compound.  Ordinarily  there  is  no  evidence  of  such 
an  intermediate  compound  and  the  process  may  be  represented  by  the 
equation, 

2RHgX  +  2NaOH  +  Na2SnO2  ->  R2Hg  +  Na2Sn03 
+  Hg  +  2NaX  +  H20. 

The  process  apparently  differs  from  the  corresponding  inorganic- 
reaction  in  that  all  of  the  mercury  does  not  appear  as  metal  even  when 
an  excess  of  sodium  stannite  is  used.116a  The  sodium  stannite  reaction 
has  been  applied  successfully  in  the  following  cases: — 

(a)  Ethyl  mercuric  chloride.117 

(b)  Ethanol  mercuric  bromide,118  Br  —  Hg  —  CH2  —  CH2  —  OH, 
gives  metallic  mercury  and  a  volatile  toxic  substance  of  carbylamine 
odor.    This  is  probably  Hg(CH2  —  CH2  —  OH)2,  although  it  has  not 
been  analyzed. 

(c)  The  action  with  the  ethyl  ether  di-mer curie  bromide  has  al- 
ready been  mentioned. 

(d)  Diepi-iodhydrine-dimercuric  bromide, 

0  — CH2 

/  \ 

BrHg  —  CH2  —  CH  CH  —  CH2  —  HgBr, 

\  / 

CH2  — 0 

obtained  from  allyl  alcohol  and  mercuric  salts  reacts  with  sodium 
stannite  giving  a  red  precipitate  which  may  be  a  mercurous  compound. 
This  immediately  turns  gray  from  the  separation  of  mercury  leaving 

0 CH2 

/  \ 

/  \ 

/  \ 

the  compound  CH  —  CH2  —  Hg  —  CH2  —  CH. 

\  / 

\  /  l^i 

\  / 

CH2 O 

ma  Stieglitz,  Kharasch,  and  Hanke,  1.  c. 

117  Dimroth,  Ghent.  Zentr.  1901  I  451. 

""Sand,  Ber.  34  (1901),  1394.  , 


64  COMPOUNDS  OF  MERCURY 

(e)  Phenyl  mercuric  chloride  gives  a  black  precipitate  with  sodium 

stannite.    No  odor  of  mercury  diphenyl  is  noticed  until  this  precipitate 

turns  gray  from  the  separation  of  mercury.119 

(f  )   o-Anisole  mercuric  iodide  12°  gives  the  corresponding  mercury 

dianisyl. 

(g)  Mercurated  nitro-  and  dinitro-benzoic  acids.121 

(h)  Cineol  mercuric  chloride  gives  mercury  dicineolyl.122 

(i)  The  reaction  has  also  been  applied  to  a  number  of  hydroxy  - 

carboxylic,  hydroxy  arsonic,  and  hydroxy  sulfonic  acids  of  benzene, 

toluene  and  naphthalene.123 

Sodium  amalgam  in  alcohol  or  even  in  dry  benzene  changes  some 

organomerouric  salts  to  the  R2Hg  compounds.     Pentamethylene  di- 

mercuric  bromide  gives  cyclomercuripentamethylene, 

\  CH2  —  CH2 

/  \ 

CH2  Hg, 

\  / 

CH2  —  CH2 

and  its  polymers.124  Phenyl  mercuric  iodide  and  acetate  give  mercury 
diphenyl.125  a-Naphthyl  mercuric  iodide  gives  mercury  dinaphthyl.126 

Sodium  metal  can  be  used  in  place  of  sodium  amalgam  in  some 
cases.  The  thiophene  mercuric  chlorides  are  changed  to  mercury  di- 
thienyls  by  heating  in  xylene  with  sodium.  This  is  the  only  method 
for  making  the  p-mercury  dithienyls.127 

Recent  patents  involve  the  use  of  such  alkaline  reducing  agents 
as  ferrous  hydroxide  or  sodium  hydrosulfite  in  the  presence  of  sodium 
hydroxide.  These  reagents  appear  to  be  better  for  preparing  the  R2Hg 
compounds  in  the  cases  of  mercurated  aromatic  acids  and  phenols. 

A  number  of  special  methods  for  making  the  mercury  compounds 
of  the  type  R2Hg  have  been  used  in  individual  cases.  Thus  methyl 
mercuric  iodide  when  distilled  with  potassium  hydroxide  or  calcium 

"•Dimroth,  loc.  clt.  449.     Dimroth,  Ber.  35   (1902),  2853. 


121  D.  R.  P.  249,725,  and  251,332.     Chcm.  Zentr.  1912  II  1413.     Frankol,  670. 
»»Sand  and  Singer,  Ber.  35  (1902),  3176. 
123  D.  R.  P.  255,030.     Chem.  Zentr.  1913  I  353. 
«*Hilpert  and  Grtittner,  Ber.  47  (1914),  186. 
""Dreher  and  Otto,  Ann.  154  (1870),  115. 
128  Hilpert  and  Grtittner,  loc.  cit.  188. 

»»Steinkopf  and  Bauermeister,  Ann.  403  (1914),  57.     Steinkopf,  Ann.  413  (1917), 
328. 


GENERAL  PROPERTIES  AND  REACTIONS  65 

hydroxide  gives  a  small  yield  of  mercury  dimethyl.128  Phenyl  mer- 
curic chloride  heated  with  dry  silver  oxide  gives  mercury  diphenyl.129 
Phenyl  mercuric  iodide  heated  in  alcohol  with  copper  bronze  gives  mer- 
cury diphenyl  in  good  yield.130 

Phenyl  mercuric  acetate  reacts  with  ammonium  hydroxide  giving  a 
substance  (C6H5Hg)2NH2OAc.  This  reacts  with  various  sulfur  com- 
pounds such  as  carbon  disulfide  and  aromatic  thioureas  giving  mercury 
diphenyl,  mercuric  sulfide  and  other  products.131 

V.    The  Reaction  Between  Organic  Mercury  Compounds   of  the 
Type  R2Hg  and  Mercuric  Salts. 

R2Hg  +  HgX2-^2RHgX. 

This  reaction  takes  place  readily  with  all  kinds  of  mercury  compounds 
even  in  the  case  of  the  mercury  a-dithienyls  and  mercuric  iodide  in 
which  case  the  reaction  goes  so  easily  in  the  opposite  direction.  The 
reaction  sometimes  takes  place  in  the  cold  but  in  general  the  substances 
have  to  be  heated  in  alcohol  or  acetone  solution.  The  reaction  has 
only  been  carried  out  with  salts  of  monobasic  acids  such  as  the  mer- 
curic halides,  cyanide,  sulfocyanate  and  organic  salts  like  the  acetate. 
It  has  been  carried  out  with  the  following  organomercuric  com- 
pounds:— 

(a)  Mercury  dimethyl.132 

(b)  Mercury  diethyl.133    Frankland's  method  of  making  ethyl  mer- 
curic chloride  from  zinc  ethyl  and  an  excess  of  mercuric  chloride  really 
involves  this  reaction  as  a  smaller  amount  of  mercuric  chloride  gives 
mercury  diethyl. 

(c)  Alcoholic  solutions  of  mercury  diethyl 134  and  mercuric  chloride 
give  an  immediate  precipitate  of  ethyl  mercuric  chloride. 

(d)  Mercury  di-isoamyl.135 

(e)  Mercury  di-cyclohexyl.136 

(f )  Cyclomercuripentamethylene 137  and  its  polymers  in  benzene 

""Buckton,  Ann.  108   (1858),  104. 

129  Otto,  J.  prakt.  Chem.  (2)   1   (1870),  184. 

iso  whitmore,  unpublished  results. 

^Pesci,  Gaze.  chim.  ital.  39  I   (1909),  150. 

132Buckton,  loc.  cit.  105. 

""Frankland,  Ann.  Ill   (18597,  60. 

""Frankland  and  Duppa,  J.  Chem.  Soc.  16   (1863),  415. 

^Frankland  and  Duppa,  loe.  cit.  422.     Ann.  130   (1864),  114. 

136Gruttner,  Ber.  47  (1914),  1655. 

and  Griittner,  Ber.  47  (1914),  191. 


66  COMPOUNDS  OF  MERCURY 

solution  readily  act  with  ether  solutions  of  the  mercuric  halides  giving 
precipitates  of  the  corresponding  pentamethylene  di-mercuric  halides. 

CH2  —  CH2  CH,  —  CH2  —  HgX 

XX  / 

CH2  Hg  +  HgX2  ->  CH, 

\  /  \ 

CH2  —  CH2  CH2  —  CH2  —  HgX 

(g)  Mercury  diphenyl 138  reacts  easily  with  mercuric  salts  in  al- 
cohol or  acetone.  Thus  a  mixture  of  mercury  diphenyl  and  the  cal- 
culated amount  of  mercuric  iodide  refluxed  with  a  little  alcohol  until 
the  color  of  the  iodide  disappears  gives  a  quantitative  yield  of  pure 
phenyl  mercuric  iodide.  Mercury  diphenyl  heated  with  mercurous 
chloride  at  160°  gives  phenyl  mercuric  chloride  and  metallic  mercury. 
The  reaction  between  mercury  diphenyl  and  mercuric  thiocyanate  re- 
quires a  temperature  of  120°. 

(h)  The  homologs  of  mercury  diphenyl  give  the  reaction.  In  some 
cases  the  mixtures  have  to  be  heated  with  alcohol  in  sealed  tubes  to 
complete  the  process.139 

(i)  Mercury  dibenzyl.140 

(j)  Mercury  di-anilines.141 

(k)  Mercury  di^anisoles  and  di-pthenetoles.142 

(1)  a-Mercury  dinaphthyl 143  does  not  react  with  mercuric  chloride 
when  heated  in  carbon  disulfide.  The  original  substances  are  recovered. 
The  reaction  however  takes  place  easily  in  alcohol  and  acetone.  Thus 
1  gm.  of  the  mercury  dinaphthyl  is  suspended  in  50  c.c.  of  hot  acetone 
and  treated  with  .6  gm.  of  mercuric  chloride.  All  goes  into  solution. 
The  addition  of  water  precipitates  the  naphthyl  mercuric  chloride. 

(m)  (3-Mercury  dinaphthyl 144  reacts  with  mercuric  halides  in  hot 
amyl  alcohol. 

338  Otto,  loc.  cit.  180.  Dreher  and  Otto,  Ann.  154  (1870),  113.  Steinkopf,  Ann.  413 
(1917),  313. 

139  Otto,  loc.  cit.  185.     Michaelis,  Ber.  28  (1895),  589. 

140  Wolff,  B&r.  46    (1913),  65.     Jones  and  Werner,  J.  Am.   Chem.  Soc.  40    (1918), 
1268. 

141  Michaelis  and  Rabinerson,  Ber.  23   (1890),  2342.     Pesci,  Ga-zz.  chim.  ital.  23  II 
(1893),  532.     Chem.  Zentr.  1894  I  501.     Oazz.  chim.  ital.  28  II    (1898),  106.     Chem. 
Zentr.  1898  II  546.     Z.  anorg.  Chem.  17  (1898),  280.     Whitmore,  J.  Am.  Chem.  Soc.  41 
(1919),  1853. 

142  Michaelis    and    Rabinerson,    loc.    cit.    2345.      Dimroth,    Ber.    32     (1899),    764. 
Michaelis,  Ber.  27  (1895),  257. 

143  Otto  and  Mories,  Ann.    147    (1868),   179.     Otto,  Ann.   154    (1870),   190.     Otto, 
J.  prakt.  Chem.  (2)   1   (1870),  185.     Steinkopf,  Ann.  413  (19X7),  313,  330. 

»*»  Michaelis,  loc.  cit,  251, 


GENERAL  PROPERTIES  AND  REACTIONS  67 

(n)  All  mercury  dithienyl  compounds  145  react  with  mercuric  ha- 
lides  in  acetone  giving  the  corresponding  thiophene  mercuric  halides 
which  can  be  precipitated  by  the  addition  of  water. 

VI.    The  Reaction  with  Halogens. 

As  has  already  been  stated,  the  compounds  R2Hg  react  with  halo- 
gens giving  an  organic  halide  and  R  —  Hg  —  X  which  can  react  with 
more  halogen  giving  more  of  the  organic  halide  and  a  mercuric  halide, 
according  to  the  equations, 

RJHg  +  X,  =  R  —  X  +  RHgX 
RHgX  +  X2  =  R  — X  +  HgX2. 

The  reaction  has  been  carried  out  with  the  following  compounds: 

(a)  Mercury  dimethyl.146 

(b)  Methyl  mercuric  acetate.147 

(c)  Mercury  diethyl  catches  fire  in  chlorine  gas.     It  reacts  less 
violently  with  bromine  and  iodine.148 

(d)  Ethyl  mercuric  hydroxide  reacts  with  bromine  forming  ethyl 
mercuric  bromide.149 

(e)  Mercury  di-n-propyl.150 

(f)  Mercury  di-isobutyl.151 

(g)  Mercury  di-sec-butyl,  formed  by  the  reduction  of  methyl  ethyl 
ketone  with  a  mercury  cathode,  reacts  with  iodine  in  ether  solution 
giving  the  corresponding  butyl  mercuric  iodide  and  butyl  iodide.152 

(h)  Mercury  di-isoamyl.153 

(i)  Mercury  dioctyl.154 

(j)  Allyl  mercuric  iodide  reacts  quantitatively  with  iodine  giving 
allyl  iodide.  This  reaction  is  used  in  separating  allyl  iodide  from 
isopropyl  iodide.  The  former  gives  a  crystalline  compound  when 
treated  with  mercury  while  the  latter  does  not.  The  purified  mercury 
compound  is  then  treated  with  iodine  to  make  pure  allyl  iodide.155 

146  Steinkopf,  loc.  cit.  313. 

146Buckton,  Ann.  108  (1858),  104.  Frankland  and  Duppa,  J.  Ghem.  Soc.  16  (1863), 
417.  Hilpert  and  Ditmar,  Ber.  46  (1913),  3740. 

147  Otto,  Ann.  154   (1870),  199. 

148Buckton,  Ann.  112  (1859),  221.  J.  prakt.  Chem.  (1)  79  (1860)  107.  Chapman, 
J.  Chem.  Soc.  19  (1866),  150. 

148Diinhaupt,  J.  prakt.  Chem.  (1)  61  (1854),  425.     Ann.  92  (1854),  379. 
150Cahours,  Compt.  rend.  76   (1873),  135,  749.     Ber.  6   (1873),  567. 
151Cahours,  J.  prakt.  Chem.  (2)   8   (1873),  398.     Compt.  rend.  77   (1873),  1405. 
•    i52Tafel>  Ber    39   (1906),  3631. 

«>3  Frankland  and  Duppa.  J.  Chem.  Soc.  16  (1863),  421.    Ann.  130   (1864),  112. 

«*Eichler,  Ber.  12   (1879),  1881. 

105  Linnemann,  Ann.  Spl.  3  (1865),  262. 


68  COMPOUNDS  OF  MERCURY 

(k)  lodomethylmercuric  iodide  reacts  with  iodine  giving  methy- 
lene  iodide.156 

(1)  Chloromethyl  mercuric  iodide  prepared  from  the  above  iodo 
compound  by  mercuric  chloride  reacts  with  iodine  giving  methylene 
chloroiodide.157 

(m)  p-Acetoxymercuriethyl  methyl  ether  obtained  from  the  action 
of  ethylene  on  mercuric  acetate  in  methyl  alcohol  solution  decolorizes 
an  ether  solution  of  iodine  instantly.  The  products  have  not  been 
studied.158 

(n)  Ethanolmercuric  iodide  obtained  from  ethylene  and  an  aqueous 
solution  of  a  mercuric  salt  reacts  with  iodine  dissolved  in  potassium 
iodide  giving  a  60%  yield  of  ethylene  iodohydrine.159  The  formation 
of  the  iodohydrine  could  also  be  explained  by  the  "molecular  formula" 
for  the  mercurated  ethylene,  C2H4.Hg(OH)L  The  basic  mercuric 
iodide  would  act  with  iodine  forming  hypoiodous  acid  which  would 
then  add  to  the  ethylene. 

(o)  Diethylether  di-mercuric  iodide,  also  obtained  from  ethylene, 
reacts  with  iodine  in  potassium  iodide  solution  giving  a  90%  yield  of 
|3|3'-di-iodo  diethyl-ether.160 

(p)  Di-epi-iodohydrine  di-mercuric  iodide  obtained  from  allyl  al- 
cohol reacts  with  iodine  giving  di-epi-iodohydrine,161 

0  — CH2 
/  \ 

I  _  CH2  —  CH  CH  —  CH2  —  I. 

\  / 

CH2  — 0 

In  this  case  the  reaction  is  carried  out  in  benzene  in  a  sealed  tube  at 
140°. 

(q)  Trichloromercuri-acetaldehyde(?),  obtained  from  acetylene 
and  mercuric  chloride,  reacts  with  chlorine  water  giving  mercuric 
chloride  and  chloral  which  is  identified  by  changing  it  to  chloroform. 
Iodine  gives  an  entirely  different  reaction  but  the  organic  product  has 
not  been  identified.162 

(r)  The  products  obtained  from  acetylene  and  mercuric  chromate, 

""Sakurai,  J.  Chem.  Soc.  37   (1880),  660. 

"'Sakurai,  J.  Chem.  Soc.  41   (1882),  360. 

1MSchoeller  and  Schrauth,  Ber.  46   (1913),  2867. 

189  Sand,  Ber.  34   (1901),  1388.  . 

160  Ibid.  1391.     Sand,  Ber.  34  (1901),  2908. 

181  Sand,  loc.  cit.  1393. 

«2Biltz  and  Mumm,  Ber.  37  (1904),  4423. 


GENERAL  PROPERTIES  AND  REACTIONS  69 

chlorate,  and  fluorsilicate  react  with  iodine  giving  iodoform  readily.163 
Mercury  acetylide  acts  with  iodine  giving  diiodoacetylene.164  When 
mercury  acetylide  is  treated  with  mercuric  chloride  it  gives  the  same 
white  precipitate  which  is  obtained  from  acetylene  and  mercuric  chlo- 
ride (trichloromercuri-acetaldehyde  ?).  This  gives  no  diiodoacetylene 
with  iodine.165 

The  product  from  phenyl  acetylene  and  mercuric  salts  reacts  with 
bromine  giving  a  product  which  may  be  dibromoacetophenone  but 
which  has  not  been  actually  identified.166 

(s)  Mercury  bis-monochloroacetylene  reacts  with  an  ethereal  solu- 
tion of  iodine  giving  chlorotriiodoethylene.167 

(t)  Mercury  bis-trichloroethylene  reacts  writh  chlorine  only  in 
strong  sunlight.  It  gives  mercuric  chloride  and  perchloroethane.168 

(u)  The  product  from  acetone  and  mercuric  oxide, 

HOHg  —  CH  —  Hg  —  CH  —  HgOH 
CH3  — C 0  —  C  — CH3 

OH      OH 

reacts  with  bromine  in  potassium  bromide  solution  giving  an  oil  having 
a  sharp  odor.  When  this  is  steam  distilled  and  treated  with  hydroxyl- 

NOH 

amine  it  gives  monomethyl  glyoxime,  CH3  —  C  —  CH  =  NOH,  indi- 
cating that  the  brominated  oil  is  unsymmetrical  dibromoacetone.169 

HgO 

(v)  Anhydro   hydroxymercuri   nitroacetic    ester,   C=N  =  0  ,   re- 

CO2Et 

acts  with  bromine  giving  dibromo  nitro  acetic  ester.170 

(w)  Mercury  diazoacetic  ester  reacts  with  iodine  giving  yellow 

163Nieuwland  and  Maguire,  J.  Am.  Cliem.  Soc.  28  (1906),  1026. 
«*Keiser,  Am.  Oh&m.  J.  15  (1893),  537. 
165  Plimpton  and  Travers,  J.  Chem.  Soc.  65   (1894),  267. 

i8«Manchot  and  Haas,  Ann.  399  (1913),  143.  Biltz  and  Reinkober,  Ann.  404 
(1914),  233. 

167  Hof ma'nn  and  Kirmreuther,  Ber.  42   (1909),  4235. 

168  IMd.  4232. 

16»Auld  and  Hantzsch,  Ber.  38    (1905),  2683. 
170Scholl  and  Nyberg,  Ber.  39  (1906),  1957. 


70  COMPOUNDS  OF  MERCURY 

mercuric  iodide.     No  gas  is  evolved.     The  organic  product  is  explo- 


sive. 


(x)  Chloromercuriformic  methyl  ester  reacts  with  iodine  in  ether 
giving  a  solution  which  apparently  contains  iodoformic  ester  as  treat- 
ment with  ammonia  gives  a  68%  yield  of  methyl  urethane.172  The 

dliyl  compound  gives  a  similar  result.    A  compound  having  a  C Hg 

grouping  identical  with  that  in  this  ester  is  the  compound, 
Et02C  —  N  —  Hg  —  C02Et 

Et02C  — N  — Hg-C02Et 

obtained  from  mercuric  oxide  and  hydrazine  monocarboxylic  ethyl 
ester,  NH2  —  NH  —  C02Et.  Treatment*  with  bromine  in  benzene  gives 
bromoformic  ester  which  is  recognized  by  its  lachrymatory  properties 
and  by  its  conversion  into  ethyl  urethane.  The  other  organic  product 
of  the  bromination  is  azodicarboxylic  ester.173 

(y)  The   di-iodide    of   anhydro   tri-hydroxymercuri    acetic    acid, 
Hgl 

C  —  Hgl  ,  reacts  with  iodine  giving  iodoform.174 

_r 

S 

0 

(z)  (3-Mercuribis-propionic  ester  decolorizes  a  warm  alcoholic  solu- 
tion of  iodine  at  once.  The  organic  products  have  not  been  identified.175 
The  corresponding  mercurated  acid  reacts  with  iodine  in  potassium 
iodide  giving  a  dark  crystalline  precipitate  which  acts  like  a  periodide. 

(a')  Pentamethylene  di-mercuric  iodide  reacts  with  iodine  in  ben- 
zene only  on  long  boiling.  It  forms  pentamethylene  di-iodide.176  Cy- 
clomercuripentamethylene  reacts  with  bromine  and  iodine  giving  pen- 
tamethylene di-mercuric  bromide  and  iodide.177  This  result  is  at  vari- 
ance with  the  usual  course  of  the  reaction  of  R2Hg  compounds  with 
halogens.  If  the  cyclomercuripentamethylene  is  really  a  six  membered 


171Buchner,  Ber.  28  (1895),  219. 

172Schoeller  and  Schrauth,  Ber.  46   (1913),  2874. 

173Diels  and  Uthemann,  Ber.  53   (1920),  729. 

174  Sand  and  Singer,  Ber.  36   (1903),  3709. 

175  E.  Fischer,  Ber.  40   (1907),  388. 
"«Hilpert  and  Grttttner,  Ber.  47   (1914),  182. 
MT  Hid.  190. 


GENERAL  PROPERTIES  AND  REACTIONS  71 

ring  containing  mercury  the  product  would  be  expected  to  have  only 
one  mercury  in  the  molecule.  There  is  no  explanation  of  the  failure 
of  this  reaction  to  take  place  in  the  usual  way.  There  seems  to  be 
no  doubt  that  the  dimercurated  compounds  are  obtained  as  they  have 
been  identified  by  analysis  and  by  mixed  melting  point  determinations 
with  the  known  bromide  and  iodide.  Both  of  the  polymers  give  the 
same  results  with  iodine  as  the  simple  substance. 

Hg-C6H5 

(b')    Pentamethylene    di-mercuriphenyl,  (CH2)5  ,    reacts 

XHg-C,H5 

with  a  benzene  solution  of  iodine  at  35°  giving  pentamethylene  di- 

Hg  — C 

mercuric  iodide.178    Pentamethylene  di-mercuriacetylide  (CH2)5 

.      \ 

Hg  — C 

reacts  quickly  with  iodine  in  hot  benzene  forming  mercuric  iodide, 
pentamethylene  di-iodide  and  di-iodoacetylene.178 

(c')  Phenyl  mercuric  compounds  react  readily  with  halogens  in 
the  usual  way.179 

(d')  The  tolyl  mercuric  chlorides  react  with  bromine  giving  o-  and 
p-tolyl  bromides.180 

(e')  Mercurated  nitrobenzenes  react  with  bromine  forming  the  cor- 
responding bromonitrobenzenes.181 

(f)  The  monomercurated  phenols  give  ortho  and  para  iodophenols 
with  an  ether  solution  of  iodine.  Mercurated  p-cresol  gives  similar 
results.182 

(g')  The  mercurated  nitrophenols  react  with  bromine  and  iodine 
giving  the  corresponding  bromo-  and  iodonitrophenols.183 

(h')  Mercurated  benzoic  acid  reacts  with  bromine  in  potassium 
bromide  solution  giving  the  potassium  salt  of  o-bromobenzoic  acid  thus 

178Hilpert  and  Griittner,  Ber.  47   (1914),  184. 

"'Otto,  J.  prakt.  Chem.  (2)  1  (1870),  182.  Dreher  and  Otto,  Ann.  154  (1870), 
108.  Soderback,  Ann.  419  (1919),  273. 

180  Dreher  and  Otto,  Ann.  154  (1870),  173.     Dimroth,  Ber.  32  (1899),  761. 

181  Dimroth,  Ber.  35   (1902),  2037.     Kharasch  and  Chalkley,  J.  Am.  Chem.  Soc.  43 
(1921),  611. 

182  Dimroth,  Ber.  31    (1898),  2155;   35    (1902),  2359.     Brieger,  Arch.  Pharm.   250 
(1912),  62.     Chem.  Zentr.  1912  I  753. 

183Hantzsch  and  Auld,  Ber.  39  (1906),  1114. 


72  COMPOUNDS  OF  MERCURY 

proving  that  the  mercury  enters  the  ortho  instead  of  the  meta  po- 
sition.184 

(V)  Mercurated  salicylic  acid  is  proved  to  have  the  mercury  in 
the  position  ortho  to  the  hydroxyl  group  by  treating  it  with  iodine 
and  then  fusing  the  iodosalicylic  acid  obtained  with  potassium  hydrox- 
ide. The  product  is  pyrocatechol-o-carboxylic  acid.185 

(j')  In  determining  the  position  of  mercuri  groups  in  anilines  it  is 
advisable  to  change  the  anilines  to  the  corresponding  acetanilides  be- 
fore treatment  with  iodine  or  bromine.186  If  this  is  not  done  more 
halogens  may  enter  the  nucleus  than  the  number  corresponding  to 
the  mercuri  groups  originally  present.  Thus  "phenylated  white  pre- 
cipitate" gives  a  mixture  of  mono-  and  diiodoanilines  although  it  con- 
tains but  one  mercury  in  the  molecule.187 

(k')  Acetoxymercuriphenylglycine  ethyl  ester  reacts  with  bromine 
and  iodine  giving  compounds  which  probably  have  the  halogen  in  the 
ortho  position.188 

(!')  The  mercurated  quarternary  ammonium  compounds  obtained 
from  the  mercurated  anilines  and  alkyl  halides  react  with  an  excess  of 
bromine  giving  the  corresponding  mercury-free  bromides.189  Thus 
[Cl  (CH3)  3N  —  C6H4  — ]  2Hg  reacts  with  bromine  giving 
C1(CH3)3N  — C6H4  — Br. 

(m')  Phenacylmercuric  chloride  gives  bromoacetophenone.190 

(n')  The  mercurated  nitrotoluenes  containing  the  groups 

Hg  HgCl 

/      \  / 

—  CH  0          and          —  CH 

\      /  \ 

Hg  HgCl 

react  with  halogens  giving  the  corresponding  benzal  halides.191  When 
these  are  boiled  with  sodium  carbonate  they  are  converted  into  the  cor- 
responding nitrobenzaldehydes. 

(o')  Mercurated  anthranilic  acid  has  the  mercury  in  the  para  po- 

^Dimroth,  B&r.  35   (1902),  2871. 

188J6id.  2873. 

««Dimroth,  B&r.  35  (1902),  2040.  Vecchiotti,  Gazz.  cMm.  ital.  44  II  (1914),  37. 
Schoeller,  Schrauth,  and  Rother,  Ber.  45  (1912),  2817.  J.  Rother,  Dissert.,  Berlin, 
1911,  p.  45  and  58. 

187  Rudolph,  B&r.  11   (1878),  78.     J.  Rother,  loc.  cit.  16. 

188  Schoeller,  Schrauth,  and  Goldacker,  B&r.  44   (1911),  1302. 

"Tesci,  Gkusz.  cMm.  ital.  23  II  (1893),  526.     Z.  anorg.  Chem.  15   (1897),  208. 
"ODimroth,  Ber.  35  (1902),  2870. 
191Reissert,  B&r.  40   (1907),  4213. 


GENERAL  PROPERTIES  AND  REACTIONS  73 

sition  to  the  amino  group  as  is  proved  by  converting  it  to  the  iodo 
compound.192  This  difference  from  the  result  of  mercurating  salicylic 
acid  is  interesting. 

(p')  a-Mercury  dinaphthyl  reacts  with  iodine  and  bromine  in  the 
usual  way.  The  first  iodonaphthalene  was  prepared  in  this  way.193 

(q')  Mercurated-|3-naphthol  carboxylic  acid  is  changed  to  the  iodo 
compound  easily.194 

(r')  a-Thiophene  mercuric  chloride  does  not  act  with  iodine. 

(s')  The  corresponding  act'  dimercurated  thiophene  readily  forms 
di-iodothiophene.  When  the  dimercurated  compound  is  refluxed  with 
bromine  water  it  gives  a  mixture  of  di-,  tri-  and  tetra  brominated  thio- 
phenes.195  a'-iodo-ct-thiophene  mercuric  chloride  gives  di-iodothio- 
phene.196 

(f)  Mercurated  camphor  reacts  with  iodine  in  benzene  giving  di- 
iodo-camphor  which  can  be  changed  to  camphor  quinone.197  The  same 
product  is  obtained  with  iodine  chloride  or  iodine  bromide.198 

(u')  Cineol  mercuric  iodide  on  treatment  with  an  ether  solution 
of  iodine  in  the  cold  gives  a  liquid  iodide  which  may  be  cineol  iodide.199 

VII.    Reaction  with  Halides  and  Cyanides  of  Metals. 

The  reaction  of  iodides  in  forming  compounds  of  the  form  R2Hg  has 
already  been  discussed  under  IV.  The  other  reactions  of  metallic 
halides  may  be  divided  into  two  classes,  those  which  result  in  a  simple 
metathesis  and  those  which  result  in  the  splitting  of  the  C  —  Hg 
linkage.  The  substances  which  have  their  C  —  Hg  linkages  broken 
are  of  two  types,  mercuration  products  obtained  by  simple  substitu- 
tion, and  mercuration  products  obtained  by  the  addition  of  the  groups 
-  HgX  and  —  OH  to  an  unsaturated  acid. 

RHgX  +  KI  +  H20  -»  R  —  H  +  HgL  +  KOH 

R  _  CHOH  —  CH  (Hgl)  —  C(XK  +  KI  -» 

R  —  CH  =  CH  —  CO2K  +  HgI2  +  KOH 

In  either  case  one  molecule  of  base  is  formed  for  each  C  —  Hg  linkage 
broken. 

U2Schoeller  and  Hueter,  Ber.  47   (1914),  1938. 

183  Otto,  Ann.  154  (1870),  189. 

1MBrieger  and  Schulemann,  J.  prakt.  Chem.  (2)  89  (1914),  176. 

195Volhard,  Ann.  267   (1892),  180. 

U8Steinkopf  and  Bauermeister,  Ann.  403   (1914),  62,  69. 

19T  Marsh  and  Fleming-Struthers,  J.  Chem.  Soc.  95  (1909),  1786. 

198  Marsh,  J.  Chem.  Soc.  97   (1910),  2413. 

189  Sand  and  Singer,  Ber.  35  (1902),  3177. 


74  COMPOUNDS  OF  MERCURY 

The  simple  metathetical  reaction  is  very  useful  in  preparing  the 
organomercuric  halides  from  the  more  soluble  compounds  such  as  the 
acetates,  nitrates,  and  sulfates.  In  many  cases  in  which  mercuric  ace- 
tate is  the  mercurating  agent  the  resulting  acetate  is  so  soluble  that  it 
cannot  be  isolated.  In  these  cases  the  original  reaction  mixture  is 
treated  with  sodium  chloride  solution  which  precipitates  the  corre- 
sponding chloride.  This  method  has  received  the  widest  application  to 
cases  varying  from  the  mercuration  products  of  ethylene  to  those  of 
the  most  complicated  naphthalene  dye  intermediates.  Whenever  the 
alkali  halides  are  to  be  used  for  these  precipitation  reactions  the  other 
two  possible  results  must  be  kept  in  mind.  For  instance  thiophene 
mercuric  chloride  treated  with  sodium  iodide  would  be  expected  to 
give  the  iodide.  In  reality,  considerable  of  the  R2Hg  compound,  mer- 
cury dithienyl,  is  obtained.  The  reaction  may  fail  in  a  different  way 
when  applied  to  a  substance  like  diacetoxymercurimalonic  ester.  In- 
stead of  the  expected  di-iodide  the  product  is  malonic  ester,  the 
C  —  Hg  linkages  being  split  entirely. 

The  splitting  of  the  C  —  Hg  linkage  by  alkali  halides  takes  place 
most  readily  with  the  inorganic  iodides.  The  bromides  act  very  little 
in  this  way  and  the  chlorides  almost  not  at  all.  Only  a  few  types  of 
organic  mercury  compounds  undergo  this  splitting.  Among  these 
are  mercury  derivatives  of  malonic  ester  and  malonic  acid,  and  cyano- 
acetic  acid.200  In  sharp  contrast  to  the  behaviour  of  these  compounds 
is  the  fact  that  mercurated  nitroacetic  ester  is  unchanged  by  potassium 
iodide.201  The  mercuration  products  of  many  unsaturated  acids  are 
changed  to  the  original  unsaturated  acids  by  the  action  of  potassium 
iodide.  The  acids  which  have  been  studied  in  this  way  are  acrylic  acid, 
crotonic  acid,  maleic  acid,  citraconic  acid,  and  itaconic  acid.205  The 
mercurated  anhydro  compounds  of  these  acids  show  an  interesting  dif- 
ference in  their  action  with  chlorides  and  iodides.  Although  the  an- 
hydrides are  insoluble  in  water  they  readily  dissolve  in  solutions  of 
chlorides  or  iodides  giving  neutral  and  strongly  alkaline  solutions  re- 
spectively. The  difference  may  be  illustrated  by  the  acrylic  acid  com- 
pound 

*>o  Biilmann,  Ber.  35  (1902),  2581.  Biilmann  and  Witt,  Ber.  42  (1909),  1070. 
Petterson,  J.  prakt.  Chem.  (2)  86  (1912),  4G4. 

201  Scholl  and  Nyberg,  Ber.  39  (190G),  1957. 

202  Biilmann,  loc.  cit.  2571.     Ber.  43  (1910),  574. 


GENERAL  PROPERTIES  AND  REACTIONS  75 

CH2OH  —  CH  —  C  =  O  +  NaCl  -»  CH2OH  —  CH  —  CO2Na 

Hg— O  HgCl 

CH2OH  —  CH  —  C  =  0  +  4NaI  -» 

Hg  — 6 

CH2  =  CH  —  C02Na  +  Na2HgI4  +  NaOH 

In  the  second  case  a  titration  with  standard  acid  shows  the  pres- 
ence of  .86  equivalent  of  base  indicating  that  the  splitting  of  the 
C  —  Hg  linkage  is  almost  quantitative.  This  reaction  is  shown  only 
by  the  addition  products  of  unsaturated  acids.  The  unsaturated  hy- 
drocarbons and  alcohols  give  addition  products  which  react  with  in- 
organic iodides  giving  complex  iodides  of  great  stability.  In  the  case 
of  the  products  from  ethylene  the  iodides  can  even  be  recrystallized 
from  hot  alkalies  without  decomposition. 

The  mercurated  phenols  are  decomposed  by  boiling  with  potas- 
sium iodide  solution.  Titration  shows  almost  exactly  one  equivalent 
of  alkali  formed  for  each  C  —  Hg  linkage.203  Potassium  bromide 
gives  the  same  splitting  to  a  limited  extent  while  potassium  chloride 
does  not  give  it  at  all.  When  the  phenolic  hydroxyl  is  no  longer  pres- 
ent as  in  the  corresponding  acetylated  phenols,  iodides  no  longer  cause 
any  splitting  of  the  C  —  Hg.  This  allows  play  to  the  other  impor- 
tant iodide  reaction,  namely,  the  formation  of  the  R2Hg  compounds. 
Thus  the  acetylated  phenol  mercuric  chlorides  react  with  an  excess 
of  potassium  iodide  giving  the  corresponding  acetylated  mercury  di- 
phenols.  These  different  reactions  may  be  illustrated  by  the  equations: 

HO— C6H4— HgCl  +  4KI  +  H,0->C6H5OH  +  KCl  +  K2HgI4+#0# 
2AcO— C6H4— HgCl  +  4KI->  ( AcO— C6H4— )  2  Hg  +  2KC1  +  K2HgI4. 

In  sharp  contrast  to  the  action  of  the  mercurated  phenols  the  mer- 
curated nitrophenols  give  no  action  with  potassium  iodide.204 

Mercurated  benzoic  acid  is  split  by  sodium  halides  with  the  forma- 
tion of  sodium  hydroxide.  .The  iodide  has  the  greatest  effect  and  the 
chloride  the  least.205 

Anhydro  p-hydroxymercuri-anthranilic  acid  is  said  to  be  soluble  in 
potassium  iodide  but  less  soluble  in  potassium  bromide  and  still  less 
in  potassium  chloride.  This  is  hard  to  understand  if  the  solubility 

203Whitmore  and  Middleton,  J.  Am.  CJiem.  8oc.  43  (1921),  622. 
a^Hantzsch  and  Auld,  Ber.  39   (190G),  1110. 
i,  Gazz.  chim.  ital.  32  II   (1902),  277. 


76  COMPOUNDS  OF  MERCURY 


\ 


depends  merely  on  a  salt  formation  as  it  usually  does, 

\_C02K 
ing 


giv- 


It  may  be  that  the  increased  solubility  in  iodides  indicates  a  split- 
ting of  the  C  —  Hg  and  a  corresponding  formation  of  alkali.206 

The  mercuration  products  of  the  naphthol  and  naphthylamine  in- 
termediates of  the  dye  industry  are  almost  all  split  by  alkali  halides.207 
In  many  cases  the  extent  of  the  splitting  has  been  measured  by 
titrations  of  the  base  formed.  In  others  the  "loosening"  effect  of  the 
halide  has  been  detected  by  means  of  ammonium  sulfide.  In  many 
cases  the  mercurated  compound  gives  no  action  with  ammonium  sulfide 
but  if  treated  with  a  halide  and  then  with  the  sulfide  gives  mercuric 
sulfide  almost  immediately.  Both  methods  of  study  show  that  the 
splitting  effect  increases  from  chloride  to  iodide. 

A  number  of  miscellaneous  observations  of  the  action  of  halides 
may  be  mentioned.  lodomethyl  mercuric  iodide,  I  —  CH2  —  Hgl,  if 
heated  with  potassium  iodide  gives  a  brown  insoluble  substance  and  a 
sublimate  of  methyl  mercuric  iodide.208  Methylene  di-mercuric  iodide 
gives  the  same  reaction  with  potassium  iodide.209  Ethylene  di-mer- 
curic iodide,  IHg  —  CH2  —  CH2  —  Hgl,  obtained  from  ethane  hexa- 
mercarbide  is  partly  soluble  in  an  excess  of  potassium  iodide  solution. 
In  sunlight  this  solution  gives  some  mercuric  iodide.210  The  reaction 
has  not  been  further  studied.  The  cyclic  mercury  compounds  obtained 
indirectly  from  ethylene  and  allyl  alcohol, 

CH2  —  CH2  O-  -CH2 

O  Hg  and  CH  —  CH2  —  Hg  —  CH2  —  CH, 

\  /  \  / 

CH2  —  CH2  "  CH2—  —0  ' 

are  unchanged  by  prolonged  heating  with  potassium  iodide.211 

2°«  Schoeller  and  Hueter,  Ber.  47  (1914),  1936. 

2OTBrieger  and  Schulemann,  J.  prakt.  Chem.   (2)   89   (1914),  105. 

2°<»Sakurai,  J.  Chem.  Soc.  39   (1881,),  487.  209  Ibid. 

2l0Hofmann,  Ber.  33  (1900),  1339.  2n  Sand,  Ber.  34   (1901),  2914. 


GENERAL  PROPERTIES  AND  REACTIONS  77 

Ethane  hexamercarbide  reacts  with  cold  solutions  of  alkali  halides 
giving  the  salts  C2HgG02X2  and  bases.  In  this  case,  this  does  not 
indicate  a  splitting  of  the  C  —  Hg  linkage.  The  soluble  base  is  formed 
by  the  action  of  the  halides  on  the  insoluble  base  forming  still  more 
insoluble  salts.212 

Stannous  chloride  reacts  with  mercury  dimethyl  forming  a  crystal- 
line compound.213  When  this  is  treated  with  water  it  gives  a  soluble 
tin  compound  and  a  precipitate  of  methyl  mercuric  chloride. 

Potassium  cyanide  has  a  splitting  effect  on  the  C  —  Hg  linkage  in 
many  cases  in  which  the  iodides  do  not.  Thus  the  ethanol-mercuric 
compounds  and  the  ethyl  ether  mercuric  compounds  obtained  from 
ethylene  react  with  cyanide  solutions  giving  ethylene  as  soon  as 
warmed.214 

In  sharp  contrast  to  the  action  of  diethylether  di-mercuric  halides 
is  the  action  of  the  cyclic  mercury  compound  obtained  from  them  by 

CH2  — CH2 
/  \ 

sodium  stannite  solution,  O  Hg.    This  substance  is  not 

\  / 

CH2  — CH2 

changed  by  potassium  cyanide  solution  even  on  prolonged  boiling.215 
The  mercury  compounds  obtained  from  allyl  alcohol  are  not  decom- 
posed by  potassium  cyanide.216 

The  mercury  compounds  obtained  from  di-cyclopentadiene  by  ad- 
dition of  the  groups  — HgCl  and  — OCH3  or  — OC2H5  react  with 
boiling  potassium  cyanide  solution  forming  di-cyclopentadiene.21T 

Ethane  hexamercarbide  on  boiling  with  potassium  cyanide  loses 
one-third  of  its  mercury  forming  the  compound,  Hg  =  C  —  C  =Hg. 218 

I         I 

CN  — Hg    Hg  — CN 
Tetra-acetoxymercuri-di-acetone  hydrate 

OH  OH 


(AcOHg)  2CH  —  C  —  0  —  C  —  CH  (HgOAc)  2, 

ATT  A-rr 

VyJl3  ^"^-3 

reacts  with  potassium  cyanide  giving  acetone.219 

212Hofmann,  Ber.  33  (1900),  1335.  213  Buckton,  Ann.  108  (1858),  105. 

21*Hofmann  and  Sand,  Ber.  33  (1900),  1344.       215  Sand,  Ber.  34  (1901),  2914, 

216  Hof  raann  and  Sand,  loc.  cit.  1359  and  2700.     Sand,  loc.  cit  2915. 

217  Hofmann  and  Seller,  Ber.  39   (1906),  3188. 
218Hofmann,  Ber.  33   (1900),  1338. 

219  Sand  and  Genssler,  Ber.  36  (1903),  3703, 


78  COMPOUNDS  OF  MERCURY 

The  mercurated  acetic  acids  and  acetaldchydes  react  with  warm 
potassium  cyanide  giving  potassium  acetate  and  acetaldehyde  re- 
spectively.220 Mercury  bis-monochloroacetylene  reacts  rapidly  with 
potassium  cyanide  giving  monochloroacetylene.221  Mercury  bis-tri- 
chloroethylene  acts  only  slowly  with  cyanide  solutions.  The  bro- 
mine compounds  act  the  same  as  the  chlorides. 

VIII.    The  Reaction  with  Halides  of  Non-Metals. 

This  reaction  is  almost  the  only  one  in  which  the  organic  com- 
pounds of  mercury  exactly  parallel  those  of  zinc  and  magnesium.  Even 
in  this  case  the  mercury  compounds  are  less  reactive. 

Boron  trichloride  reacts  giving  mercuric  halides  and  compounds 
of  the  type  R  —  BC12.  It  reacts  with  mercury  diphenyl,  mercury  di- 
tolyls,  and  mercury  dinaphthyl  only  on  heating  to  about  150°. 222  On 
the  other  hand  it  reacts  in  the  cold  with  mercury  di-anisoles  and 
mercury  diphenetoles.223 

Phosphorus  trichloride  reacts  with  mercury  dimethyl  forming 
methyl  mercuric  chloride.224  With  mercury  dipropyl  it  forms  tripropyl 
phosphine.225  Allyl  mercuric  iodide  does  not  react  with  phosphorus 
tribromide  even  on  heating.226 

In  general  aromatic  mercury  compounds  react  with  phosphorus 
trichloride  at  a  high  temperature  giving  the  dichloro  aromatic  phos- 
pines,  R  —  PC12.  The  reaction  has  been  carried  out  with  phenyl,  o- 
and  p-tolyl,  xylyl,  p-anisyl,  and  p-phenetyl  mercury  compounds.227 
Phosphenyl  chloride,  C0H5PC12  reacts  with  p-tolyl  mercuric  bromide 
giving  p-tolyl  phenyl  chlorophosphine.228  * 

Arsenic  trichloride  reacts  with  mercury  dipropyl  giving  tripropyl 
arsine.229  Mercury  diphenyl  and  phenyl  mercuric  chloride  react  with 
arsenic  trichloride  giving  phenyl  dichloroarsine.230  Mercury  dithienyj 

22°Hofmann,  Ber.  31  (1898),  1908  and  2213;  32  (1899),  875;  37  (1904)  4460. 
Hofmann  and  Kirmreuther,  Ber.  42  (1909),  4237. 

221Hofmann  and  Kirmreuther,  loc.  cit.  4233.     Ber.  41   (1908),  317. 

222  Michaelis  and  Becker,  Ber.  13  (1880),  59  and  180.  Michaelis,  Ber.  27  (1894), 
247. 

228  IUa.  254. 

224Buckton,  Ann.  108  (1858),  105. 

22BCahours,  Ber.  6  (1873),  568. 

226  Oppenheim,  Ber.  4  (1871),  671. 

227  Michaelis,  Ann.  293   (1896),  196,  248,  257,  291,  303,  313. 

228  Pope  and  Gibson,  J.  Chem.  Soc.  101  (1912),  737. 
229Cahours,  loc.  cit.  568. 

230 Michaelis,  Ann.'  201  (1880),  197  and  217.  Roeder  and  Blasi,  Ber.  47  (1914), 
2748. 


GENERAL  PROPERTIES  AND  REACTIONS  79 

and  thiophene  mercuric  halides  react  smoothly  to  form  the  thiophene 
arsenic  compounds  of  the  types  R  —  AsCl2  and  R2AsCL231 

The  reaction  of  sulfur  monochloride  with  organic  mercury  com- 
pounds has  been  studied  only  in  the  case  of  ethane  hexamercarbide 
and  its  salts.232  C2Hg0Cl6  will  not  act  even- at  120°.  The  base, 
C2HgG04H2  reacts  with  a  10%  solution  of  sulfur  monochloride  in  ben- 
zene giving  a  yellow  compound  containing  only  four  atoms  of  mercury, 

(ClHg)2C-C(HgCl)2. 


u 


Thionyl  chloride  reacts  with  mercury  aromatic  compounds  giving 
the  corresponding  aromatic  mercuric  chloride.236  Recently  it  has  been 
found  that  thionyl  chloride  will  react  with  anhydro  hydroxymercuri- 
benzoic  acid  giving  the  mercurated  acid  chloride.237 

Cl 

—  C=0  -0  =  0 

\      +  SOC12  =  +  S0 

-HgO 


Thionyl  chloride  is  said  to  react  on  a-mercury  dinaphthyl  with  the 
formation  of  p-naphthyl  chloride.238 

IX.    Reaction  with  Alkyl  and  Aryl  Halides. 

The  heating  of  an  alkyl  mercuric  iodide  with  an  alkyl  iodide  might 
be  expected  to  give  mercuric  iodide  and  a  lengthened  carbon  chain. 
However,  such  is  not  the  case.  There  are  only  two  instances  in  which 
a  reaction  like  this  is  known  to  take  place  and  neither  one  of  them 
involves  an  alkyl  halide.  When  benzal  chloride  is  heated  with  mercury 
diphenyl  some  triphenyl  methane  is  obtained.239  When  allyl  mercuric 
iodide  is  heated  with  allyl  iodide  the  product  is  "probably"  diallyl.240 
In  view  of  the  fact  that  allyl  mercuric  iodide  when  heated  alone  gives 
diallyl  this  action  is  not  very  significant. 

231FinzI,  Ga«z.  chim.  ital.  45  II  (1915),  283.  Chem.  Zentr.  1916  I  474.  Stelnkopf, 
Ann.  413  (1917),  317. 

232Hofmann  and  Feigel,  Ber.  38  (1905),  3655. 

NOTE.  —  Reference  numbers  233,  234  and  235  arc  omitted. 

238Mj0feaelts  and  Godchaux,  Ber.  24   (1891),  758. 

237  Sachs,  Ber.  53  (1920),  1740. 

238  Heumann  and  Kochlin,  Ber.  16    (1883),  1626. 
239Kekul6  and  Franchimont,  Ber.  5   (1872),  907. 
240  Linnemann,  Ann.  Spl.  3  (1865),  262. 


80  COMPOUNDS  OF  MERCURY 

When  mercury  diethyl  is  heated  with  allyl  iodide  in  a  tube  at  120° 
for  two  days  the  products  are  ethyl  mercuric  iodide,  ethyl  iodide,  and 
diallyl.241  These  products  could  be  explained  by  assuming  that  allyl 
iodide  on  heating  tends  to  give  iodine  and  diallyl.  The  iodine  would 
act  on  the  mercury  diethyl  giving  the  observed  products.  In  a  similar 
way  mercury  diethyl  reacts  with  iodoform  at  100°  giving  acetylene, 
ethylene,  ethyl  iodide  and  ethyl  mercuric  iodide.  This  complex  re- 
action is  all  the  more  remarkable  in  that  it  starts  even  at  70°. 242  Mer- 
cury diethyl  does  not  react  with  cold  bromoacetic  ethylester  but  when 
heated  to  150°  gives  a  gas  which  is  "probably"  ethylene.  The  other 
products  are  ethyl  mercuric  bromide  and  ethyl  acetate.243 

Methylene  dimercuric  iodide  heated  with  ethyl  iodide  or  bromide 
at  140°  gives  methyl  mercuric  iodide.244 

Ethane  hexamercarbide  heated  with  ethyl  iodide  and  ether  for  60 
hours  at  90°  gives  C2Hg6I6  and  a  small  amount  of  mercuric  iodide. 
The  volatile  products  have  not  been  studied.245 

Mercury  diphenyl  heated  with  ethylene  dibromide  at  200°  for  8 
hours  gives  phenyl  mercuric  bromide.  No  other  product  has  been 
identified.246 

Mercury  malonic  ester  gives  no  mercuric  iodide  even  on  long  boil- 
ing with  ethyl  iodide.247 

Mercury  diazoacetic  ester  reacts  very  little  with  methyl  iodide  even 
at  120°. 248 

a-Mercury  dinaphthyl  is  unchanged  after  heating  with  ethyl  iodide 
several  hours  at  160°  ,249 

Thiophene  mercuric  chlorides  do  not  react  with  alkyl  halides  or 
with  halogen  esters.250 

When  an  alkyl  halide  reacts  with  a  compound  obtained  from  mer- 
curic salts  and  an  unsaturated  compound  it  usually  gives  the  original 
unsaturated  compound.  Thus  ethanol  mercuric  iodide  Vhen  heated 
with  methyl  iodide  gives  mercuric  iodide,  ethylene,  and  methyl  alcohol. 
The  same  substance  heated  with  chloroform  at  150°  gives  mercuric 

2«Suida,  Monatsh.  1  (1880),  714. 

*"Il>id.  716. 

243  Sell  and  Lippmann,  J.  prakt.  Chem.  (1)  99  (1866),  432. 

^Sakurai,  J.  Chem.  Soc.  39  (1881),  487. 

2«Hofmann,  Ber.  33  (1900),  1335. 

^Dreher  and  Otto,  Ann.  154   (1870),  128. 

^Schoeller  and  Schrauth,  Ber.  41   (1908),  2090. 

»8Buchner,  Ber.  28  (1895),  219. 

249  Otto  and  Mories,  Ann.  147    (1868),  178, 

^Volhard,  Ann.  267  (1892),  174. 


GENERAL  PROPERTIES  AND  REACTIONS  81 

iodide  and  chloride  and  a  "non-gaseous  unsaturated  compound."251 
Di-epi-iodohydrine  di-mercuric  iodide  obtained  from  allyl  alcohol  can 
be  crystallized  unchanged  from  hot  benzyl  chloride.252  The  mercury 
compound  obtained  from  allylene  reacts  with  ethyl  iodide  at  100°  giv- 
ing a  variety  of  products  among  others,  mercuric  iodide,  ethyl  chloride, 
and  ethyl  ether.253 

The  mercurated  formic  esters  obtained  from  carbon  monoxide  and 
alcoholic  solutions  of  mercuric  acetate  react  with  methyl  or  n-propyl 
iodide  at  100°  giving  carbon  monoxide,  mercuric  iodide,  and  an  alco- 
hol.25* This  reaction  is  hard  to  understand  if  the  structure  of  these 
substances  is  as  indicated.  On  the  other  hand,  the  fact  that  these 
iodides  do  not  give  higher  esters  is  no  evidence  against  the  structure 
formula  as  organic  mercury  compounds  do  not  react  with  alkyl  halides 
to  give  lengthened  carbon  chains. 

Methyl  iodide  reacts  normally  with  mercurated  anilines  forming 
the  corresponding  quarternary  ammonium  compounds.255 

Methyl  iodide  also  reacts  normally  with  the  sodium  compounds  of 
mercurated  phenols  giving  the  corresponding  mercurated  anisoles.256 

Phenyl  iodidechloride,  C6H5IC12,  reacts  with  organic  mercury  com- 
pounds as  if  dissociated  into  phenyl  iodide  and  chlorine.  Thus  mer- 
cury diethyl  gives  ethyl  mercuric  chloride,  ethyl  chloride,  and  phenyl 
iodide.257  In  the  presence  of  metallic  sodium  the  reaction  takes  a  dif- 

C6H5 
\ 

ferent  course  giving  I  —  Cl. 

/ 
C2H5 

X.    Reaction  with  Acid  Halides. 

Organomercuric  halides  might  be  expected  to  react  with  acid  halides 
forming  mercuric  halides  and  ketones.  As  with  alkyl  halides  this  re- 
action fails  with  practically  all  organic  mercury  compounds.  The  only 
mercury  compounds  which  give  ketones  with  acid  chlorides  are  the 

"'Hofmann  and  Sand,  Ber.  33  (1900),  1349. 
*>Sand,  Ber.  34  (1901),  1393. 
263  Kutscheroff,  Ber.  17  (1884),  21. 
2MManchot,  Ber.  53  (1920),  984. 

2MPesci,  Gazz.  chim.  ital.  23  II  (1893),  532,  537.     Ruspaggiari,  Ibid.  546.     Chem. 
Zentv.  1894  I  501.     Pesci,  Z.  anorg.  Chem.  15  (1897),  219. 
268  Dimroth,  Ber.  32  (1899),  764. 
367  Willgerodt,  Ber.  30  (1897),  57;  31  (1898),  921. 


82  COMPOUNDS  OF  MERCURY 

a-mono-mercurated  thiophenes.  These  react  with  acetyl  chloride  and 
benzoyl  chloride  forming  acetthienone  and  thiophene  phenyl  ketone.258 
The  reaction  with  acetyl  chloride  is  likely  to  become  violent.  The  best 
yield  of  the  ketone  is  obtained  by  using  thiophene,  acetyl  chloride,  and 
a  small  amount  of  the  a-thiophene  mercuric  chloride  as  a  catalyst. 
In  some  cases  this  process  gives  a  better  yield  than  the  Friedel-Crafts 
reaction.  The  mercurated  thiophenes  do  not  react  with  succinyl  chlo- 
ride or  phosgene.  The  dimercurated  thiophenes  do  not  react  with  any 
acid  chloride. 

Allyl  mercuric  iodide  does  not  react  with  acetyl  or  benzoyl  chloride 
even  on  heating.259  Mercury  malonic  ester  gives  no  mercuric  chloride 
even  on  long  boiling  with  acetyl  chloride.260 

Mercury  compounds  containing  amino  or  hydroxyl  groups  can  be 
acylated  without  affecting  the  mercury.  A  number  of  mercurated 
anilines  have  been  acetylated.261  The  ortho  and  para  mercurated 
phenols  can  be  acetylated^by  cold  acetyl  chloride.262  o-Chloromercuri- 
dinitrophenol  does  not  give  an  acetyl  derivative  but  gives  a  small  yield 
of  a  benzoyl  derivative  by  the  Schotten-Baumann  reaction.263 

The  mercury  addition  products  of  ethylene  compounds  can  be  ben- 
zoylated.  Thus  ethanolmercuric  iodide  obtained  from  ethylene  gives 
a  benzoate,  IHg  —  CH2  —  CH20  —  COC6H5.264  Propylene  glycol  mer- 
curic iodide,  prepared  from  allyl  alcohol,  gives  a  dibenzoyl  derivative, 

CH20  —  COC6H5 
CHO  —  COCRH  *65 


CH,— 


When  the  aromatic  sulfonyl  chlorides  react  with  organic  mercury 
compounds  they  give  little  or  none  of  the  expected  sulfones.  Thus 
mercury  diphenyl  heated  with  benzene  sulfonyl  chloride  in  benzene 
solution  at  160°  gives  a  complicated  reaction.  Small  amounts  of  phenyl 

2MVolhard,  Ann.  267  (1892),  178.  Steinkopf  and  Bauermeister,  Ann.  403  (1914), 
58. 

889  Oppenheim,  B&r  4    (1871),  671. 

2«°  Schooner  and  Schrauth,  Ber.  41  (1908),  2090. 

181  Dimrotii",  Ber.  35  (1902),  2040.  J.  Rother,  Dissert.,  Berlin,  1911,  pp.  45  &  58. 
Schoeller,  Schrauth,  and  Rother,  Ber.  45  (1912),  2817.  Vecchiotti,  Gazz.  chfan.  ital. 
44  II  (1914),  37.  Chem.  Zentr.  1914  II  1350. 

282  Whitmore  and  Middleton,  J.  Am.  Chem.  Boc.  43  (1921),  619. 

263Hantzsch  and  Auld,  Ber.  39  (1906),  1113. 

284  Sand,  Ber.  34  (1901),  1390. 

26BJ6id.  1393. 


GENERAL  PROPERTIES  AND  REACTIONS  83 

mercuric  chloride  and  diphenyl  sulfone  are  obtained.266  Mercury  di- 
phenyl  heated  with  p-toluene  sulfonyl  chloride  at  120°  for  fifteen 
hours  gives  an  almost  quantitative  yield  of  p-tolyl  mercuric  chloride 
and  a  mere  trace  of  a  sulfone.267  The  sulfonyl  chlorides  do  not  react 
with  the  mercurated  thiophenes,  as  do  the  acyl  chlorides.268 

The  reaction  of  the  sulfide  of  o-mercuribenzoyl  chloride  with 
methyl  alcohol  has  already  been  discussed  under  section  III.269 

Two  compounds,  the  action  of  which  may  be  considered  here,  are 
chloroformic  ester  and  chlorocyanogen.  The  former  of  these  substances 
gives  "no  satisfactory  result"  with  mercury  di-p-cymene  and  the  lat- 
ter gives  no  action  at  all.270  Chloroformic  ester  reacts  in  the  cold 
with  mercury  diazoacetic  ester  giving  mercurous  chloride  and  a  thick 
oil  which  liberates  nitrogen  on  treatment  with  an  acid.271  The  mer- 
curated thiophenes  give  no  action  when  heated  in  a  sealed  tube  with 
cyanogen  chloride.272 

XI.    Reaction  with  Metals. 

Mercury  dialkyls  and  diaryls  react  with  many  metals  on  heating, 
giving  organic  compounds  of  these  metals.  In  some  cases  the  metal 
does  not  enter  the  reaction  and  the  only  change  is  a  thermal  decompo- 
sition of  the  mercury  compound  giving  metallic  mercury  and  a  hydro- 
carbon according  to  the  equation, 

R2Hg  heated  =  Hg  +  R  —  R. 

The  metals  which  behave  in  this  way  are  copper,  silver,  gold  and 
iron.273 

The  reaction  of  sodium  with  compounds  of  the  type  R  —  Hg  —  Cl 
has  already  been  mentioned  in  section  IV  under  methods  of  making 
R2Hg.274  Sodium  reacts  with  mercury  dimethyl,  diethyl,  and  diphenyl 
giving  the  corresponding  sodium  organic  compounds.275  The  reaction 

288  Otto,  Ber.  18   (1885),  246. 

267  Otto,  loc.  cit.  249. 

2«8Steinkopf  and  Bauermeister,  Ann.  403  (1914),  59. 

2«9  Sachs,  Ber.  53  (1920),  1740. 

I70Paterno  and  Colombo,  Ber.  10  (1877),  1749. 

^Buchner,  Ber.  28  (1895),  219. 

272Volhard,  Arm. '267  (1892),  175. 

^Frankland  and  Duppa,  J.  Chem.  Soc.  17  (1864),  36.  Ann,  130  (1864),  125.  Otto 
and  Mories,  Ann.  147  (1868),  179.  Dreher  and  Otto,  Ann.  154  (1870),  129. 

274Steinkopf  and  Bauermeister,  loc.  cit.  57.     Steinkopf,  Ann.  413   (1917),  328. 

^Bucktonv  J.  prakt.  Ch&m.  (1)  79  (1860),  107.  Chapman,  J.  Ghent.  Soc.  19 
(1866),  150.  Dreher  and  Otto,  Ann.  154  (1870),  116  and  129.  Acree,  Am.  Chem.  J. 
29  (1903),  588.  Schorigin,  Ber.  41  (1908),  2719.  Hilpert  and  Griittner,  Ber.  46 
(1913)  1679. 


84  COMPOUNDS  OF  MERCURY 

of  mercury  diethyl  with  sodium  has  been  used  in  making  sodium  ethyl 
for  use  in  synthetic  work.276 

Beryllium  (glucinum)  reacts  with  mercury  diethyl  and  dipropyl 
giving  the  corresponding  beryllium  dialkyls.277  Magnesium  gives  sim- 
ilar reactions  with  mercury  methyl  and  phenyl.278 

The  action  of  zinc  with  mercury  compounds  has  been  studied  more 
carefully  than  that  of  any  other  metal.  It  gives  zinc  dialkyls  and 
diaryls  readily.  In  fact  the  best  method  of  making  many  organic  zinc 
compounds  is  to  make  the  mercury  compound  first  and  then  heat  it 
with  zinc.279  The  mercury  compounds  which  have  been  found  to  re- 
act with  zinc  are  those  of  the  following  groups:  (a)  Methyl  and 
ethyl,280  (b)  n-Propyl,281  (c)  Isobutyl,282  (d)  Isoamyl,283  (e)  Phenyl.284 

a-Mercury  dinaphthyl  in  carbon  disulfide  does  not  react  with  zinc  in 
the  cold.285 

Cadmium  reacts  with  mercury  dimethyl,  diethyl,  and  diphenyl  at  a 
high  temperature  giving  some  thermal  decomposition  and  a  partial 
formation  of  cadmium  organic  compounds.286 

Aluminum  reacts  with  mercury  dimethyl,  diethyl,  and  dipropyl 
giving  the  corresponding  aluminum  trialkyls.287  It  reacts  vigorously 
with  mercury  diphenyl  giving  aluminum  triphenyl.288 

Bismuth  reacts  with  mercury  diethyl  and  diphenyl  giving  a  partial 
transformation  into  the  bismuth  ethyl  and  phenyl  compounds.289 

™  Schorigin,  Bcr.  41   (1908),  2723;  43   (1910),  1938. 
2"Cahours,  Compt.  rend.  76   (1873),  1383. 

278  Fleck,  Ann.  276   (1893),  130.     Hilpert  and  Gruttner,  loc.  cit.  1677. 

279  Franklaud    and    Duppa,    J.    Chem.    Soc.    17    (1864),    30.      Marquardt,    Bcr.    21 
(1888),  2038. 

28<>  Frankland  and  Duppa,  Ann.  130  (1864),  118.  J.  Chem.  Soc.  17  (1864),  29. 
Chapman,  J.  Chem.  Soc.  19  (1866),  150.  Lohr,  Ann.  261  (1891),  75. 

281Cahours,  Compt.  rend.  76  (1873),  751.     Ber.  6  (1873),  568. 

282Cahours,  J.  prakt.  Chem.  (2)  8  (1873),  398. 

2«»  Frankland  and  Duppa,  loc.  cit. 

284  Hilpert  and  Gruttner,  Ber.  46  (1913),  1675.  Dreher  and  Otto,  Ann.  154 
(1870),  129. 

28BOtto  and  Mories,  Ann.  147  (1868),  179. 

280  Frankland  and   Duppa,   loc.   cit.   125  and   36.     Lohr,   loc.   cit.   61.     Hilpert  and 
Gruttner,  loc.  cit.  1675. 

28IBuckton  and  Odling,  Ann.  8pl.  4  (1865),  110  ff.  Cahours,  Compt.  rend.  76 
(1873),  135,  752.  Ber.  6  (1873),  568. 

288  Hilpert  and  Gruttner,  Ber.  45   (1912),  2829. 

289  Hilpert  and  Gruttner,  Ber.  46   (1913),   1675.     Frankland  and   Duppa,   loc.   cit. 
125  and  36. 


Chapter  IV. 
Alkyl  Mercury  Compounds. 

Methyl  Mercury  Compounds. 

Mercury  Dimethyl 
Preparation. 

1.  From  methyl  iodide  and  sodium  amalgam.1    Methyl  iodide  does 
not  react  with  sodium  amalgam  at  ordinary  temperatures  even  on  long 
standing.    As  soon  as  a  little  ethyl  or  methyl  acetate  is  added  reaction 
starts  with  a  considerable  evolution  of  heat.    The  catalytic  action  of 
the  ester  is  not  understood. 

Ten  parts  of  methyl  iodide  and  one  part  of  methyl  acetate  are 
treated  in  the  cold  with  an  excess  of  dilute  sodium  amalgam  (about 
1  :  500).  The  flask  must  be  provided  with  an  efficient  upright  con- 
denser and  usually  must  be  cooled  during  the  more  violent  part  of  the 
reaction.  The  reaction  is  complete  when  a  sample  tested  with  nitric 
acid  gives  no  iodine.  If  the  mixture  becomes  too  thick  from  the  sepa- 
ration of  sodium  iodide  it  may  be  distilled  from  the  water  bath  and 
the  distillate  may  be  treated  with  fresh  amalgam.  At  the  end  of 
the  reaction  the  methyl  acetate  is  distilled  off  for  use  in  later  runs. 
The  residue  is  treated  with  water  and  distilled  from  an  oil  bath  at  a 
temperature  not  above  110°.  The  distillate  consists  of  two  layers. 
The  lower  layer  is  shaken  with  concentrated  potassium  hydroxide  to 
remove  traces  of  methyl  acetate  and  then  washed  with  water  and  dis- 
tilled. B.P.  93-96°. 

2.  From  methyl  mercuric  iodide  and  zinc  dimethyl.2 

3.  From  methyl  mercuric  iodide  and  potassium  cyanide.3 

A  mixture  of  the  solids  is  subjected  to  dry  distillation.    The  distil- 

JFrankland   and   Duppa,  J.    CJiem.   Soc.   16    (1863),   415.     Ann.    130    (1864),   117. 
Otto,  Ann.  154  (1870),  198.     L.  W.  Jones,  J.  Am.  Chem.  Soc.  40  (1918),  1271. 
2Buckton,  Ann.  109   (1859),  219.     J.  prakt.  Chem.   (1)   76  (1859),  362. 
8Buckton,  Ann.  109  (1859),  218.     Ann.  108   (1858),  103. 

85 


86  COMPOUNDS  OF  MERCURY 

late  is  washed  with  water,  dried  with  calcium  chloride,  and  redistilled. 
Yield  poor. 

4.  From  methyl  mercuric  iodide  distilled  with  a  base.4 
Potassium  hydroxide  or  calcium  hydroxide  may  be  used.    The  yield 

is  even  poorer  than  by  the  cyanide  method. 

5.  From  mercuric  chloride  and  aluminum  carbide.5 

A  mixture  of  equal  weights  of  the  substances  is  added  to  water 
and  the  mixture  is  kept  slightly  acid  by  the  careful  addition  of  hydro- 
chloric acid.  Drops  .of  mercury  dimethyl  soon  separate. 

6.  From  mercuric  chloride  and  methyl  magnesium  iodide.6 

Properties.7 

Mercury  dimethyl  is  a  colorless,  strongly  refractive  liquid  with  a 
slight  sweetish  odor.  It  is  easily  inflammable.  It  is  easily  soluble  in 
alcohol  and  ether.  Its  alcoholic  solution  is  precipitated  by  the  addition 
of  water.  B.P.  93-96°.  Sp.g.  3.069.  Vapor  density  referred  to  air  8.29. 
It  crystallizes  at  the  temperature  of  evaporating  solid  carbon  dioxide. 
It  easily  dissolves  caoutchouc,  resins,  and  phosphorus  but  dissolves 
sulfur  only  slightly.  It  is  a  very  deadly  poison.8 

Reactions. 

1.  With  halogens.9 

An  alcoholic  solution  reacts  with  iodine  forming  methyl  iodide  and 
methyl  mercuric  iodide.  It  reacts  in  a  similar  way  with  bromine. 

2.  With  iodocyanogen.10 

An  ether  solution  at  50°  gives  mercuric  cyanide.  At  110°  the 
products  are  mercuric,  iodide  and  methyl  isocyanide. 

3.  With  metals. 

Sodium  reacts  with  an  alcoholic  solution  giving  metallic  mercury.11 
In  inert  solvents  sodium  forms  sodium  methyl.12  An  ether  solution 

«Buckton,  Ann.  103  (1858),  104. 

BHilpert  and  Ditmar,  Ber.  46   (1913),  3738. 

6  Private  communication  from  C.  S.  Marvel  of  the  University  of  Illinois.  Yield 
about  60  per  cent. 

TBuckton,  loc.  cit.  Seidel,  J.  prakt.  Chem.  (2)  29  (1884),  135.  Hilpert  and 
Ditmar,  loc.  cit.  Crymble,  J.  Chem.  Soc.  105  (1914),  658.  Lohr,  Ann.  261  (1891),  59. 

8Schoeller,  Schrauth,  and  Muller,  Biochem.  Z.  33  (1911),  381.  Hilpert  and 
Ditmar,  loc.  cit.  3741. 

"Frankland  and  Duppa,  J.  Chem.  800.  16  (1863),  415.  Ann.  130  (1864),  104. 
Buckton,  Ann.  108  (1858),  103.  Hilpert  and  Ditmar,  loc.  cit.  3740. 

"Calmels,  Compt.  rend.  99  (1884),  240. 

"Chapman,  J.  Chem.  800.  19  (1866),  150.     Ann.  139  (1866),  128. 

"Schlenk,  Ber.  50  (1917),  262. 


ALKYL  MERCURY  COMPOUNDS  87 

treated  with  sodium  and  carbon  dioxide  gives  a  very  small  yield  of 
sodium  acetate.13 

Magnesium  does  not  react  with  mercury  dimethyl  up  to  120°.  If 
heated  for  36  hours  at  130°  it  gives  solid  magnesium  dimethyl  and 
metallic  mercury.14 

Zinc  at  120°  gives  zinc  dimethyl.15 

Cadmium  gives  no  cadmium  organic  compounds  but  only  cadmium 
amalgam  and  ethane.16 

Aluminum  forms  aluminum  trimethyl.17 

4.  With  cadmium  iodide.18 

Heating  a  mixture  of  mercury  dimethyl  and  cadmium  iodide  gives 
a  very  little  mercuric  iodide,  mercury,  and  ethane.  No  organic  cad- 
mium compound  is  obtained. 

5.  With  acids.19 

Concentrated  sulfuric  acid  and  hydrochloric  acid  give  methane  and 
the  corresponding  methyl  mercuric  salts. 

Glacial  acetic  acid  at  250°  removes  one  methyl  group  as  methane. 
The  other  products  are  metallic  mercury  and  a  brown  amorphous 
substance.  This  reaction  differs  from  that  of  mercury  di-isoamyl  and 
mercury  dibenzyl  which  give  isoamyl  acetate  and  benzyl  acetate  re- 
spectively.20 

6.  With  stannous  chloride.21 

A  crystalline  compound  is  formed.  Water  decomposes  it  giving 
methyl  mercuric  chloride  and  a  soluble  tin  compound. 

7.  With  phosphorus  trichloride.22 

Methyl  mercuric  chloride  is  the  only  product  isolated. 

8.  With  antimony  trichloride.23 

The  reaction  takes  place  according  to  the  equation, 

2(CH3)2Hg  +  SbCl3  -*  (CH3)3SbCl2  +  CH3HgCl  +  Hg. 
The  process  involves  a  peculiar  oxidation  of  the  antimony  and  re- 
duction of  the  mercury. 

"Schorigin,  Ber.  41  (1908),  2717. 

"Lohr,  Ann.  261   (1891),  48.     Fleck,  Ann.  276   (1893),  130. 

18Frankland  and  Duppa,  Ann.  130  (1864),  117.    J.  Chem.  Soc.  17  (1864),  28. 

"Lohr,  loc.  cit. 

"Buckton  and  Odling,  Ann.  Spl.  4  (1865),  110. 

18  Lohr,  loc.  cit. 

"Buckton,  Ann.  108   (1858),  105. 

20  L.  W.  ^ones,  J.  Am.  Ch&m.  Soc.  40  (1918),  1271.     Chem.  A^st.  12   (1918),  2320. 

21  Buckton,  loc.  cit. 

22  Buckton,  loc.  cit. 
^Landolt,  Ann.  78   (1851),  91. 


88  COMPOUNDS  OF  MERCURY 

9.  With  nitrogen  peroxide.24 

Imidodihydroximic  acid  is  probably  formed.  The  reaction  differs 
from  that  of  the  aromatic  mercury  compounds  in  not  giving  any  dia- 
zonium  salts. 

10.  With  potassium  permanganate.25 

The  permanganate  is  reduced  to  manganese  dioxide  giving  a  prod- 
uct which  reacts  with  hydrochloric  acid  to  form  methyl  mercuric 
chloride.  The  intermediate  product  is  probably  methyl  mercuric  hy- 
droxide. 

11.  With  mercuric  salts.28 

Mercuric  iodide  readily  reacts  with  mercury  dimethyl  giving  methyl 
mercuric  iodide. 

Isolation  of  the  complex  metal,  CH3Hg  — ,27 

Methyl  mercuric  halides  electrolyzed  in  liquid  ammonia  solution 
give  a  fine  black  deposit  on  the  cathode.  This  deposit  is  a  good  con- 
ductor of  electricity  but  does  not  amalgamate  with  mercury.  When 
allowed  to  come  to  room  temperature  it  decomposes  suddenly  with 
evolution  of  heat,  forming  mercury  and  mercury  dimethyl.  The  free 
methyl  mercury  group  can  also  be  obtained  as  fine  black  flakes  by 
electrolyzing  a  water  or  alcohol  solution  of  methyl  mercuric  chloride. 

The  hydroxide  and  oxide  of  mercury  methyl.28 

A  solution  of  the  hydroxide  is  obtained  by  treating  methyl  mer- 
curic iodide  with  silver  oxide  and  water.  The  aqueous  solution  is 
strongly  basic.  Treatment  of  methyl  mercuric  iodide  with  potassium 
hydroxide  gives  a  solid  "methyl  mercuric  oxide"  which  is  soluble  in  an 
excess  of  base.  The  hydroxide  is  also  formed  when  potassium  per- 
manganate acts  on  mercury  dimethyl. 

Methyl  mercuric  chloride.29 
Preparation. 

1.  From  the  action  of  hydrochloric  acid  on  mercury  dimethyl.  The 
other  product  is  methane  gas.30 

"Bamberger,  Ber.  32  (1899),  3546.     Of.  Chem.  Zentr.  1898  II  1015. 
"Seidel,  J.  prakt.  Chem.   (2)  29  (1884),  134  and  136. 
M  Buckton,  loc.  cit. 

"Kraus,  J.  Am.  Chem.  Soc.  35  (1913),  1740. 

"Frankland,  Ann.  85    (1853),  363.     Dttnhaupt,  Ann.   92    (1854),   381.     J.  prakt. 
Chem.  (1)  61  (1854),  399.     Crymble,  J.  Chem.  Soc.  105   (1914),  666. 
*»  Crymble,  Ibid.  668. 
80  Buckton,  Ann.  108    (1858),  105. 


ALKYL  MERCURY  COMPOUNDS  89 

2.  From  the  action  of  water  on  the  crystalline  compound  of  stan- 
nous  chloride  with  mercury  dimethyl.31 

3.  From  mercury  dimethyl  and  phosphorus  trichloride.32 

4.  From  the  action  of  hydrochloric  acid  on  methyl  mercuric  hydrox- 
ide obtained  by  oxidizing  mercury  dimethyl  with  potassium  perman- 
ganate.33 

5.  From  aluminum  carbide  treated  with  an  excess  of  mercuric  chlo- 
ride and  an  excess  of  10  per  cent  hydrochloric  acid.     Yield  30  per 
cent.34 

6.  Probably  the  best  methods  of  preparation  would  be:   (a)  treat- 
ment of  methyl  magnesium  iodide  with  a  large  excess  of  mercuric 
chloride,  or  (b)  treatment  of  mercury  dimethyl  prepared  by  the  sodium 
amalgam  method  with  the  calculated  amount  of  mercuric  chloride  in 
alcohol. 

Properties*5 

White  crystals.  M.P.  170°.  Volatile  with  steam.  Peculiar  dis- 
agreeable odor.  (CHHgCL)  36  Density  4.063.  It  absorbs  light  less 
than  ethyl  mercuric  chloride  which  in  turn  absorbs  it  less  than  mer- 
curic chloride.  The  molecular  weight  determined  in  methyl  sulfide 
and  in  ethyl  sulfide  is  normal. 

Methyl  mercuric  bromide.    M.P.  1600.37 
Methyl  mercuric  iodide.58 
Preparation. 

1.  From  mercury  dimethyl  and  iodine  in  alcohol.39 

2.  From  methyl  iodide  and  mercury.    A  mixture  of  the  calculated 

nlbid. 
"  Ibid. 

^Seidel,  J.  prakt.  Chem.  (2)  29  (1884),  135. 
«*Hilpert  and  Ditmar,  Ber.  46  (1913),  3739. 

86  Schroder,  Ber.  12  (1879),  563.  Ley  and  Fischer,  Z.  anorg.  Chem.  82  (1913),  338. 
Crymble,  J.  Chem.  Soc.  105  (1914),  658.  Weiner,  Z.  anorg.  Chem.  15  (1897),  37. 

86  The    analyses   of   the   compounds    mentioned    will    be    indicated    by    parentheses 
enclosing  the  symbols  of  the  substances  determined  in  the  analyses.     If  no  comment 
is   made  it   will   be  understood    that   the   analyses   check   with   the   theoretical   values 
within  reasonable  limits.    Any  unusual  variations  will  be  indicated. 

87  Crymble,  lUd. 

"Frankland  and  Duppa,  Ann.  130  (1864),  107.  J.  Chem.  Soc.  16  (1863),  415. 
Crymble,  Ibid. 

88  Buckton,  loc.  cit.  103.     Frankland  and  Duppa,  loc.  cit.  416.     Hilpert  and  Ditmar, 
loc.  cit. 


90  COMPOUNDS  OF  MERCURY 

amounts  of  these  substances  turns  to  a  crystalline  mass  when  allowed 
to  stand  in  direct  sunlight  for  about  sixty  hours.40 

3.  From  a  water  solution  of  the  chloride  and  potassium  iodide.41 

Properties. 

Colorless  pearly  leaflets.  It  is  best  crystallized  from  hot  methyl 
alcohol  in  which  it  is  much  more  soluble  than  in  ether  or  ethyl  alcohol. 
It  is  insoluble  in  water,  soluble  in  ether  and  in  methyl  iodide.  It  is 
slightly  volatile  and  has  a  slight  but  peculiar  disagreeable  odor.  M.P. 
145°  (143°).  (CHHgl.) 

Methyl  mercuric  iodide  adds  to  (CH3)2SI2  giving  the  same  prod- 
uct as  is  obtained  from  (CH3)3SI  and  HgI2.42 

Methyl  mercuric  acetate.43 

Mercury  dimethyl  and  glacial  acetic  acid  heated  in  a  sealed  tube 
for  one  hour  at  120°  give  methane  and  the  acetate.  The  latter  is  puri- 
fied by  crystallization  from  hot  acetic  acid.  Satiny  rhombic  leaflets. 
It  has  a  peculiar  disagreeable  odor  and  is  practically  insoluble  in  boil- 
ing water  and  cold  acetic  acid.  It  is  more  soluble  in  hot  acetic  acid 
and  in  alcohol.  It  is  volatile  with  steam.  M.P.  142-3°.  Note.  It  is 
probable  that  the  substance  prepared  by  Otto  was  not  the  pure  acetate. 
The  substance  prepared  from  methyl  mercuric  iodide  and  silver  acetate 
has  different  properties  from  those  given  by  Otto.44 

Methyl  mercuric  nitrate.45 

The  filtrate  from  the  action  of  silver  nitrate  on  methyl  mercuric 
iodide  gives  colorless  leaflets  of  the  nitrate.  It  is  very  soluble  in 
water  but  less  so  in  alcohol.  It  melts  to  a  colorless  liquid  at  100°. 
Its  solution  gives  no  precipitate  with  base  solutions.  A  solution  treated 
with  hydrochloric  acid  or  a  chloride  solution  gives  a  precipitate  of 
methyl  mercuric  chloride. 

Methyl  mercuric  suljate46 

Prepared  from  mercury  dimethyl  and  concentrated  sulfuric  acid. 

«Frankland,  Ann.  85   (1853),  361. 
"  Hilpert  and  Ditmar,  loc.  cit.  3740. 

"Smiles,  J.  Chem.  Soc.  77   (1900),  162;  91   (1907),  1394. 
«3Otto,  Ann.  154   (1870),  199. 

*4  Unpublished  results  obtained  by  M.  C.  Sneed  and  J.  I*.  Maynard  of  the 
University  of  Minnesota. 

"Strecker,  Ann.  92   (1854),  79. 
«6Buckton,  Ann.  108   (1858),  105. 


ALKYL  MERCURY  COMPOUNDS  91 

Methyl  mercuric  sulfide.*7 

An  excess  of  methyl  mercuric  iodide  in  an  excess  of  base  reacts 
with  ammonium  sulfide  giving  a  slightly  yellow  flocculent  precipitate. 
It  has  a  peculiar  unbearable  odor.  It  may  also  be  prepared  from  a  solu- 
tion of  methyl  mercuric  chloride  in  10  per  cent  hydrochloric  acid 
treated  with  hydrogen  sulfide.  Warming  changes  the  methyl  mer- 
curic sulfide  to  mercuric  sulfide  and  mercury  dimethyl.  (S,  low.)  48 

Ethyl  Mercuric  Compounds 

Mercury  Diethyl. 
Preparation. 

1.  From  zinc  diethyl  and  dry  mercuric  chloride.49 

The  mixture  of  the  two  substances  has  to  be  cooled  at  first  to  abate 
the  violence  of  the  reaction.  When  the  reaction  slackens  the  mixture  is 
warmed  gently  and  then  distilled.  Water  is  added  to  decompose  any 
unchanged  zinc  compound. 

2.  From  zinc  diethyl  and  ethyl  mercuric  iodide.50 

The  latter  substance  is  prepared  from  ethyl  iodide  and  mercury 
in  diffused  sunlight.  It  is  dissolved  in  zinc  diethyl.  The  solution  on 
standing  soon  deposits  zinc  iodide.  The  mercury  diethyl  is  then  dis- 
tilled off. 

3.  From  zinc  diethyl  and  mercurous  chloride.51 

4.  From  ethyl  iodide  and  sodium  amalgam.52 

The  preparation  is  carried  out  exactly  as  in  the  case  of  the  methyl 
compound  except  that  ethyl  acetate  is  used  as  the  catalyst  and  the 
mixture  is  warmed  slightly. 

5.  From  ethyl  bromide  and  sodium  amalgam.53 
The  bomide  acts  as  well  as  the  iodide. 

6.  From  allyl  mercuric  iodide  and  zinc  diethyl.54 

These  substances  react  in  cold  ether  solution  forming  mercury, 

«Frankland,  Ann.  85  (1853),  363.    "Hilpert  and  Ditmar,  Ber.  46   (1913),  3740. 

48  When  an  analysis  varies  widely  from  the  theoretical  value  the  direction  of  the 
variation  will  be  indicated. 

«  Buckton,  Ann.  109   (1859),  219.     J.  prakt.  Chem.  (1)   76  (1859),  362. 

60  Buckton,  loc.  cit.  222. 

«  Buckton,  loc.  cit.  221. 

MFrankland  and  Duppa,  J.  Chem.  Soc.  16  (1863),  418.  Ann.  130  (1864),  104.' 
Otto,  Ann.  154  (1870),  198.  Hale  and  Nunez,  J.  Am,.  Chem.  Soc.  33  (1911),  1561. 
L.  W.  Jones,  J.  Am.  Chem.  Soc.  40  (1918),  1270.  Chem.  Abst.  12  (1918),  2320. 

63  Chapman,  J.  Chem.  Soc.  19   (1866),  150.     Ann.  139  (1866),  128. 

"Oppenheim,  Ber.  4  (1871),  671. 


92  COMPOUNDS  OF  MERCURY 

mercury  diethyl,  zinc  iodide,  and  diallyl.  This  reaction  is  hard  to  ex- 
plain unless  allyl  mercuric  iodide  here  undergoes  the  decomposition 
which  ordinarily  takes  place  only  at  high  temperatures  giving  diallyl, 
mercury,  and  mercuric  iodide  which  then  reacts  with  the  zinc  diethyl.55 

7.  From  methyl  mercuric  iodide  and  zinc  diethyl.56 
Distillation  of  these  substances  appears  to  give  mercury  diethyl 

and  zinc  dimethyl.  This  reaction  should  be  contrasted  with  the  action 
of  ethyl  mercuric  chloride  with  zinc  dimethyl  which  is  believed  to 
give  the  mixed  mercury  alkyl,  ethyl  mercury  methyl. 

8.  From  a-naphthyl  mercuric  bromide  and  ethyl  magnesium  bro- 
mide.57 

Here  the  mixed  compound,  ethyl  mercury  naphthyl  would  be  ex- 
pected but  is  not  obtained.  Perhaps  it  is  formed  and  then  separates 
into  mercury  diethyl  and  mercury  dinaphthyl. 

9.  From  ethyl  mercuric  iodide  and  potassium  cyanide.58 
The  dry  distillation  of  these  substances  gives  a  poor  yield. 

10.  By  the  oxidation  of  ethyl  hydrazine  by  mercuric  oxide.59 

11.  From  bismuth  triethyl  and  mercuric  chloride.60 

Properties.6* 

Mercury  diethyl  is  a  colorless  liquid  with  a  slight  hazel  odor.  B.P. 
159°.  It  is  almost  insoluble  in  water,  only  slightly  soluble  in  alcohol, 
but  readily  soluble  in  ether.  Sp.  g.  2.44.  (CHHg.)  At  low  tempera- 
tures it  turns  to  a  thick  viscous  liquid.  It  burns  readily  but  with  a  less 
luminous  flame  than  the  methyl  compound.  Exposed  to  sunlight  it 
deposits  a  white  waxy  substance  which  is  soluble  in  ether  and  in  hot 
alcohol.  Heating  decomposes  it  to  mercury,  a  combustible  -gas,  and  a 
black  carbonaceous  residue.  The  waxy  substance  has  a  strong  dis- 
agreeable odor  resembling  garlic.  When  applied  to  the  skin  it  causes 
burns  which  are  slow  to  heal.62  When  the  vapor  of  mercury  diethyl  is 
heated  a  little  above  205°  it  decomposes  with  a  slight  explosion  form- 
ing mercury  and  an  inflammable  gas.  Mercury  diethyl  is  one  of  the 

85  Linnemann,  Ann.  140  (1866),  180. 
«8Frankland,  Ann.  Ill  (1859),  57. 
87Hilpert  and  Griittner,  Ber.  48  (1915),  908. 
MBuckton,  Ann.  108  (1858),  105. 
69  E.  Fischer,  Ann.  199  (1879),  332. 

«°Dunhaupt,  J.  prakt.  CJiem.  (1)   61   (1854),  423.     Ann.  92   (1854),  379. 
61  Hale  and   Nunez,   loc.   cit.     Frankland  and   Duppa,   loc.   cit.     Buckton,   loc.   cit. 
Crymble,  loc.  cit.     Lohr,  Ann.  261   (1891),  59. 
M  Hale  and  Nunez,  loc.  cit.  1561. 


ALKYL  MERCURY  COMPOUNDS  93 

deadliest  poisons.63    Given  in  less  than  lethal  doses  it  can  be  detected 
in  the  organs  of  animals  months  after  its  administration.64 

Reactions. 

1.  With  halogens.65 

Mercury  diethyl  dropped  into  chlorine  gas  catches  fire.  Treatment 
with  iodine  or  bromine  and  water  gives  the  corresponding  ethyl  mer- 
curic halide. 

2.  With  metals.66 

Sodium  in  alcohol  gives  metallic  mercury.  Sodium  acts  with  pure 
mercury  diethyl  giving  a  gray  solid  which  is  spontaneously  inflam- 
mable. This  gray  solid  is  probably  impure  sodium  ethyl.  On  warm- 
ing it  gives  a  mixture  of  ethane  and  ethylene. 

Carbon  dioxide  acting  on  mercury  diethyl  and  sodium  in  benzene 
gives  a  12  per  cent  yield  of  sodium  benzoate.  With  toluene  the  product 
is  phenyl  acetic  acid.  Similar  reactions  have  been  carried  out  with 
m-xylene,  ethyl  benzene,  benzophenone,  methyl  benzoate,  benzalde- 
hyde,  p-cymene,  and  thiophene.  The  hydrocarbons  apparently  act 
with  the  sodium  ethyl  giving  sodium  derivatives  which  then  react  with 
the  carbon  dioxide.67 

Magnesium  yields  magnesium  diethyl  and  mercury.  The  solid 
magnesium  compound  is  even  more  inflammable  than  the  correspond- 
ing methyl  compound. 

Zinc  heated  with  mercury  diethyl  for  36  hours  at  100°  acts  more 
readily  than  it  does  with  the  methyl  compound.  It  forms  zinc  diethyl. 

Cadmium  reacts  slowly  on  heating  giving  only  a  partial  change  to 
cadmium  diethyl. 

Aluminum  reacts  at  the  temperature  of  the  water  bath  giving  alu- 
minum triethyl. 

Iron  in  the  form  of  the  reduced  powder  gives  no  action  until  heated 
hot  enough  to  give  a  thermal  decomposition  of  the  mercury  diethyl 
forming  mercury  and  butane.  No  iron  carbon  compound  is  obtained. 

«Forster,  J.  Chem.  Soc.  117  (1920),  1158. 

«*Schoeller,  Schrauth,  and  Miiller,  Biochem.  Z.  33  (1911),  403. 

«  Chapman,  J.  Chem.  Soc.  19  (1866),  150.  Ann.  139  (1866),  128.  Buckton,  Ann. 
112  (1859),  222. 

66  Buckton,  J.  prakt.  Chem.  (1)  79  (1860),  107.  Frankland  and  Duppa,  Ann.  130 
(1864),  120.  J.  Chem.  Soc.  17  (1864)  31.  Buckton  and  Odling,  Ann.  Spl.  4  (1865), 
110.  Cahours,  Compt.  rend.  76  (1873),  135  and  1384.  Jahresber.  (1873)  517. 
Schorigin,  Ber.  41  (1908),  2719  and  2725;  43  (1910),  1931.  Zeiser,  Ber.  28  (1895), 
1675.  Peters,  Ber.  41  (1908),  3174. 

87  Schorigin,  loc.  cit. 


94  COMPOUNDS  OF  MERCURY 

Copper  behaves  the  same  as  iron. 

Beryllium  gives  beryllium  diethyl. 

Bismuth  heated  with  mercury  diethyl  at  140°  gives  large  amounts 
of  bismuth  triethyl  but  the  reaction  cannot  be  brought  to  completion. 

Silver  and  gold  cause  only  a  thermal  decomposition  of  the  mercury 
diethyl. 

Zirconium  gives  no  carbon  compound  even  at  200°. 

Tellurium  gives  diethyl  telluride. 

3.  With  acids.68 

Mercury  diethyl  does  not  react  with  dilute  acids.  With  concen- 
trated hydrochloric  or  sulfuric  acid  it  yields  ethane  and  a  salt  of 
mercury  ethyl.  This  method  has  been  recommended  for  the  prepara- 
tion of  pure  ethane. 

Mercury  diethyl  heated  with  glacial  acetic  acid  at  190°  gives  ethane, 
ethylene,  metallic  mercury,  and  some  ethyl  acetate.69 

4.  With  bromoacetic  ester.70 

Refluxing  the  two  liquids  at  150°  gives  a  small  amount  of  a  gas 
which  unites  with  bromine  and  is  probably  ethylene.  After  refluxing 
for  8  hours  the  mixture  is  cooled.  Crystals  of  ethyl  mercuric  bromide 
separate.  The  mother  liquor  gives  some  ethyl  acetate.  The  reaction 
can  probably  be  represented  by  the  equation 

C2H5  —  Hg  —  C2H5  +  Br  —  CH2  —  C02Et  -> 
CH2  =  CH2  +  C2H5  —  Hg  —  Br  +  CH3  —  C02Et. 

No  explanation  of  the  reaction  has  been  suggested. 

5.  With  potassium  permanganate.71 

Heating  mercury  diethyl  with  aqueous  potassium  permanganate 
gives  manganese  dioxide  and  a  strongly  basic  solution  which  probably 
contains  ethyl  mercuric  hydroxide.  Hydrochloric  acid  precipitates 
ethyl  mercuric  chloride  from  this  solution. 

6.  With  allyl  iodide.72 

Equal  molecules  of  the  substances  heated  in  a  sealed  tube  for  two 
days  at  130°  yield  ethyl  mercuric  iodide,  ethyl  iodide,  and  diallyl. 
Apparently  the  high  temperature  causes  the  allyl  iodide  to  give  diallyl 

«>Buckton,  Ann.  112  (1859),  221.  J.  prakt.  Chem.  (1)  79  (1860),  107.  Schor- 
lemmer,  Ann.  132  (1864),  234. 

"L.  W.  Jones,  J.  Am.  Chem.  Soc.  40  (1918),  1271.       Chem.  Abst.  12  (1918),  2320. 
TOSell  and  Lippmann,  J.  prakt.  Chem.  (1)  99  (1866),  432. 
"Seidel,  J.  prakt  Chem.  (2)  29  (1884),  134. 
"Suida,  Monatsh.  1  (1880),  714. 


ALKYL  MERCURY  COMPOUNDS  95 

and  iodine  which  immediately  reacts  with  the  mercury  diethyl  giving 
the  observed  products. 

7.  With  iodoform.73 

The  reaction  starts  at  70°,  becomes  rapid  at  90°,  and  is  complete 
at  105°.  Higher  temperatures  make  it  too  rapid.  The  products  are 
acetylene,  identified  by  the  copper  and  silver  compounds  ethylene, 
identified  by  the  formation  of  ethylene  dibromide;  and  ethyl  iodide 
and  ethyl  mercuric  iodide.  The  formation  of  ethylene  is  not  very  satis- 
factorily explained  by  the  equation, 

2CHI3  +  4 (C2H5) 2Hg  =  4C2H5  -  Hg  —  I  +  2C2H5I  +  3C2H4. 

8.  With  arsenic  trichloride.74 

The  products  are  ethyl  dichloroarsine  and  ethyl  mercuric  chloride. 

9.  With  phenyl  arsenious  sulfide.75 

The  reaction  takes  place  on  heating  according  to  the  equation, 

(C2H5)2Hg  +  C6H5AsS  =  HgS  +  C6H5As(C2H5)2. 

10.  With  arsenobenzene.76 

When  the  substances  are  heated  to  150°  phenyldiethyl  arsine  and 
metallic  mercury  are  formed. 

11.  With  aromatic  iodide-chlorides.77 

When  phenyl  iodide-chloride,  C6H5IC12,  is  warmed  gently  with  mer- 
cury diethyl  a  violent  reaction  takes  place.  The  reaction  does  not 
give  the  desired  product,  ethyl  phenyl  iodonium  chloride,  but  gives 
phenyl  iodide,  ethyl  chloride,  and  ethyl  mercuric  chloride.  The  iodide- 
chloride  apparently  dissociates  into  phenyl  iodide  and  chlorine  and 
the  latter  reacts  with  the  mercury  diethyl.  WThen  a  mixture  of  phenyl 
iodide-chloride  and  mercury  diethyl  is  treated  with  metallic  sodium 
the  product  is  ethyl  phenyl  iodonium  chloride.  In  this  case  the  real 
reacting  substance  ie  probably  sodium  ethyl. 

12.  With  mercuric  salts.78 

Alcoholic  mercuric  chloride  gives  ethyl  mercuric  chloride. 

78  Suida,  loc.  cit.  723. 
74  La  Coste,  Ann.  208  (1881),  33. 
7BMichaelis  and  Schulte,  Ber.  15  (1882),  1956. 
"Michael!*  and  Schulte,  loc.  cit.  and  Ber.  14  (1881),  913. 
"Willgerodt,  Ber.  30  (1897),  57;  31  (1898),, 921. 

"Frankland  and  Duppa,  Ann.  Ill  (1859),  59;  130  (1864),  109.  J.  Chem.  Soc. 
16  (1863),  415. 


96  COMPOUNDS  OF  MERCURY 

The  complex  metal,  C2H5Hg— ,79 

This  substance  is  obtained  by  electrolysis  in  the  same  way  as  the 
methyl  compound.  On  being  compressed  by  rubbing  with  a  glass  rod 
it  takes  on  a  coppery  appearance,  thus  differing  from  the  methyl  com- 
pound which  gives  no  sign  of  metallic  luster. 

Ethyl  mercuric  hydroxide.80 

A  hot  alcoholic  solution  of  ethyl  mercuric  chloride  reacts  with  sil- 
ver oxide  forming  silver  chloride  and  a  solution  of  the  base.  Evapo- 
ration of  the  alcohol  leaves  a  colorless  oil.  It  is  very  soluble  in  alcohol 
and  water  giving  a  strongly  basic  solution.  It  burns  the  skin  like 
caustic  alkalies  and  causes  blisters  like  cantharides.  It  reacts  with 
ammonium  salts  liberating  ammonia  and  forming  the  corresponding 
ethyl  mercuric  salts.  Zinc  acts  on  the  pure  substance  giving  zinc  amal- 
gam and  zinc  diethyl.  It  precipitates  solutions  of  salts  of  zinc,  copper, 
aluminum,  iron,  tin,  gold,  and  platinum.  Cupric  and  ferric  solutions 
give  precipitates  differing  from  those  given  by  ordinary  bases.  Hydro- 
gen sufide  gives  a  white  precipitate  which  slowly  blackens  on  standing. 
Hydrobromic  acid  and  hydrocyanic  acid  react  with  the  base  forming 
salts.  Bromine  forms  ethyl  mercuric  bromide  and  the  corresponding 
bromate.  Iodine  forms  ethyl  mercuric  iodide. 
Ethyl  mercuric  chloride. 

Preparation. 

1.  From  zinc  diethyl  and  an  excess  of  mercuric  chloride.81 

2.  From  mercury  diethyl  and  mercuric  chloride.82 

A  mixture  of  the  two  substances  in  alcohol  is  heated  to  boiling  and 
filtered  hot.  On  cooling  crystals  separate.  These  are  purified  by 
dissolving  in  hot  alcohol  and  precipitating  by  adding  a  little  water. 

3.  From  ethyl  mercuric  hydroxide  obtained  by  oxidizing  mercury 
diethyl  by  potassium  permanganate.83 

4.  From  the  hydroxide  and  ammonium  chloride  solution.84 

5.  From  bismuth  triethyl  and  mercuric  chloride.85 

Mixing  the  alcoholic  solutions  gives  an  immediate  precipitate  of 

"Kraus,  J.  Amer.  Chem.  8oc.  35  (1913),  1737. 

•oDiinhaupt,  J.  prakt.  Chem.  (1)  61  (1854),  415.    Ann.  92  (1854),  379. 
"Buckton,  Ann.  109  (1859),  219.    J.  prakt.  Chem.  (1)  76  (1859),  362.    Frankland, 
Ann.  Ill  (1859)  59. 

"Frankland  and  Duppa,  Ann.  130  (1864),  109. 

«  Seidel,  loc.  cit. 

•* Diinhaupt,  J.  prakt.  Chem.  (1)  61  (1854),  428.     Ann.  92  (1854),  379. 

»/&id.  415. 


ALKYL  MERCURY  COMPOUNDS  97 

ethyl  mercuric  chloride.    Ethyl  bismuth  dichloride  remains  in  solution. 
6.  By  precipitating  a  solution  of  ethyl  mercuric  nitrate  with  a  chlo- 
ride solution.86 

Properties.87 

Silvery  iridescent  leaflets.  Difficultly  soluble  in  cold  alcohol,  readily 
soluble  hot,  slightly  soluble  in  ether,  and  practically  insoluble  in  wa- 
ter. M.P.  192.5°.  It  sublimes  easily  even  at  40°  giving  thin  colorless 
leaflets.  Density  3.5.  It  absorbs  light  less  than  mercuric  chloride  but 
more  than  methyl  mercuric  chloride.  (CHHgCl.) 

Ethyl  mercuric  chloride  is  more  toxic  than  mercury  diethyl.  The 
latter  substance  probably  changes  to  the  chloride  in  the  body.88 

Reactions. 

1.  With  zinc  dimethyl.    The  product  is  possibly  methyl  mercury 
ethyl  which  decomposes  on  distillation  giving  the  simple  mercury 
alkyls.89 

2.  With  phenyl  iodide-chloride.    No  reaction  takes  place  cold.    On 
heating  the  products  are  phenyl  iodide,  ethyl  chloride,  and  ethyl  mer- 
curic chloride.    Thus  the  iodide-chloride  acts  the  same  as  it  does  with 
mercury  diethyl,  that  is,  it  acts  like  phenyl  iodide  and  free  chlorine.90 

3.  With  metallic  zinc  forming  ethyl  zinc  chloride.91 

Ethyl  mercuric  bromide.92 
Preparation. 

1.  From  mercuric  bromide  and  bismuth  triethyl  in  alcoholic  solu- 
tion. 

2.  From  ethyl  mercuric  hydroxide  and  hydrobromic  acid  or  bro- 
mine. 

3.  From  mercury  diethyl  and  bromoacetic  ester  at  150°. 

Properties. 
Like  those  of  the  chloride.     (Br.) 

89Strecker,  Ann.  92   (1854),  78. 

87  Strecker,  loc.  cit.  Dunhaupt,  loc.  cit.  Seidel,  loc.  cit.  Frankland  and  Duppa, 
loc.  cit.  Crymble,  J.  (Them.  Soc.  105  (1914),  668.  Schroeder,  Ber.  12  (1879),  563. 
Ley  and  Fischer,  Z.  anorg.  Chem.  82  (1913),  338. 

MSchoeller,  Schrauth,  and  Miiller,  Biochem.  Z.  33  (1911),  405. 

89  Frankland,  Ann.  Ill   (1859),  59. 

90  Willgerodt,  Ber.  31  (1898),  921. 
"  Dunhaupt,  loc.  cit. 

wDttnhaupt,  loc.  cit.     Sell  and  Lippmann,  J.  prakt.  Chem.  (I)  99  (1866),  432. 


98  COMPOUNDS  OF  MERCURY 

Ethyl  mercuric  iodide. 
Preparation. 

1.  From  ethyl  iodide  and  metallic  mercury  in  diffused  light.93 

2.  From  an  alcoholic  solution  of  the  hydroxide  and  iodine.94 

3.  From  mercury  diethyl  and  allyl  iodide  heated.95 

4.  From  mercury  diethyl  heated  with  iodoform.96 

Properties.97 

Fine  white  leaflets  having  an  unpleasant  odor.  It  is  best  re- 
crystallized  from  alcohol  and  ether.  It  can  also  be  recrystallized  from 
boiling  ammonium  hydroxide  or  potassium  hydroxide.  Exposure  to 
sunlight  turns  it  yellow  and  finally  red  with  the  formation  of  mercuric 
iodide.  M.P.  182°.  (CHHgl). 

Reactions.9* 

1.  Alcoholic  silver  nitrate  gives  a  solution  of  ethyl  mercuric  nitrate. 

2.  Zinc  diethyl  changes  it  to  mercury  diethyl. 

3.  Dry  distillation  with  potassium  cyanide  gives  a  poor  yield  of 
mercury  diethyl. 

Other  ethyl  mercuric  salts. 

The  cyanide  is  prepared  from  the  hydroxide  and  concentrated  hy- 
drocyanic acid.  It  forms  good  crystals  which  are  very  volatile  and 
have  a  strong  odor.  It  appears  to  be  very  toxic.  The  cyanide  can- 
not be  isolated  from  a  mixture  of  alcoholic  mercuric  cyanide  and  bis- 
muth triethyl  although  the  repulsive  odor  of  the  mixture  would  indi- 
cate that  some  of  it  is  formed.99 

The  acetate  is  prepared  by  heating  mercury  diethyl  with  glacial 
acetic  acid  in  a  sealed  tube  at  120°  for  one  hour.  It  forms  shiny 
rhombic  leaflets,  which  can  be  recrystallized  from  hot  acetic  acid. 
Peculiar  disagreeable  odor.  M.P.  178°. 10° 

The  nitrate  can  be  made  from  alcoholic  solutions  of  the  iodide  and 

"Frankland,  Ann.  Ill  (1859),  59.  Strecker,  Ann.  92  (1854),  76.  Buckton,  Ann. 
109  (1859),  222.  J.  prakt.  Chem.  (1)  76  (1859)  362. 

94  Diinhaupt,  loc.  cit. 

95  Suida,  loc.  cit. 
88  IMd . 

^Strecker,  Ann.  92  (1854),  77.  Dtinhaupt,  J.  pralct.  Chem.  (1)  61  (1854),  425. 
Ann.  92  (1854),  379.  Crymble,  J.  Chem.  Soc.  105  (1914),  668. 

98  Strecker,   loc.   cit.     Buckton,   loc.   cit. 

99  Dtinhaupt,  loc.  cit. 

100 Otto,  Ann.  1.54  (187.0),  199. 


ALKYL  MERCURY  COMPOUNDS  99 

silver  nitrate.  Evaporation  of  the  filtrate  in  vacuo  leaves  clear  prisms 
very  soluble  in  alcohol  but  less  so  in  water.101  The  nitrate  can  also  be 
prepared  from  the  hydroxide  and  nitric  acid.  Evaporation  leaves  an 
oil  which  crystallizes  on  standing.  (CH,N205).102  A  solution  of  the 
nitrate  in  water  reacts  with  chloride  solutions  giving  a  precipitate  of 
ethyl  mercuric  chloride. 

The  sulfate  can  be  made  from  alcoholic  solutions  of  one  of  the 
halides  and  silver  sulfate.  Evaporation  of  the  filtrate  gives  silvery 
leaflets.  (CHHg,S03).103  The  sulfate  is  also  obtained  by  treating 
mercury  diethyl  with  concentrated  sulfuric  acid.104 

The  sulfide  is  obtained  by  adding  ammonium  sulfide  to  an  alcoholic 
solution  of  the  chloride.  The  precipitate  is  soluble  in  an  excess  of  the 
sulfide.  When  dried  the  precipitate  forms  a  yellow  powder  which  can 
be  crystallized  from  ether.  (CHSHg.) 

The  phosphate  is  obtained  as  a  thick  mass  soluble  in  water  by  treat- 
ing a  dilute  alcoholic  solution  of  the  chloride  with  silver  phosphate  and 
evaporating  the  filtrate.105 

The  carbonate  and  oxalate  may  be  obtained  in  the  same  way  as  the 
phosphate.  Both  are  crystalline. 

n-Propyl  Mercury  Compounds. 

Mercury  Dipropyl. 
Preparation.™6 

Normal  propyl  iodide  treated  with  an  excess  of  dilute  sodium  amal- 
gam gives  a  pasty  mass  which  is  treated  with  alkali  and  distilled  with 
steam.  The  heavy  oil  is  separated,  evaporated  on  the  steam  bath,  and 
then  distilled.  B.P.  189-91°. 

Properties.  . 

Colorless  mobile  liquid.  Almost  odorless  when  cold  but  having  a 
very  penetrating  odor  when  hot.  It  is  almost  insoluble  in  water,  solu- 
ble in  alcohol,  and  very  soluble  in  ether.  Its  density  at  16°  is  2.124. 
B.P.  189-91°. 

101  Strecker,  loc.  cit. 

102  Dunhaupt,  loc.  cit.  t 
*»  Dunhaupt,  loc.  cit. 
1MBuckton,  loc.  cit. 

wo  Dunhaupt,  loc.  cit. 

l06Cahours,  Oompt.  rend.  76  (1873),  134.  Ber.  6  (1873),  567.  JqhresT).  (1873), 
517, 


100  COMPOUNDS  OF  MERCURY 

Reactions. 

1.  With  halogens.107 

Iodine  reacts  violently  forming  propyl  iodide  and  propyl  mercuric 
iodide  or  mercuric  iodide  depending  on  the  amount  used.  Bromine 
water  is  decolorized  at  once  giving  shining  plates  of  propyl  mercuric 
bromide. 

2.  With  acids. 

It  reacts  with  the  following  acids  forming  propane  and  the  corre- 
sponding propyl  mercuric  salt:  hydrochloric,  sulfuric,  nitric,  and  acetic 
acids. 

3.  With  tripropyl  stannic  iodide  it  gives  tin  tetrapropyl. 

4.  With  metals.108 

Beryllium  in  a  sealed  tube  at  130°  quickly  forms  mercury  and 
beryllium  dipropyl.  Zinc  and  Aluminum  act  in  a  similar  way. 

Propyl  mercuric  hydroxide. 

When  propyl  mercuric  iodide  is  treated  with  moist  silver  oxide  an 
alkaline  solution  is  obtained  which  on  evaporation  leaves  a  viscous 
mass  which  gives  a  few  crystals  on  standing  in  a  vacuum  over  sul- 
furic acid.  A  solution  of  the  substance  in  water  has  strong  basic 
properties.  It  forms  salts  with  acids.  Among  the  salts  made  in  this 
way  are  the  sulfate,  nitrate,  arsenate,  tartrate,  oxalate,  and  cyanide. 

Propyl  mercuric  chloride. 

A  white  crystalline  substance  obtained  by  boiling  mercury  dipropyl 
with  hydrochloric  acid  or  by  treating  a  water  solution  of  the  base  with 
hydrochloric  acid.  It  can  be  recrystallized  from  hot  alcohol. 

Propyl  *mercuric  bromide. 

Shiny  white  plates  obtained  by  treating  mercury  dipropyl  with 
bromine  water  or  by  treating  the  base  with  hydrobromic  acid. 

Propyl  mercuric  iodide. 

Treatment  of  mercury  dipropyl  with  iodine  in  alcohol  yields  the 
iodide  which  crystallizes  from  hot  alcohol  in  pearly  scales  having  a 
very  disagreeable  odor.  It  reacts  with  moist  silver  oxide  forming  the 
hydroxide. 

""Cahours,  loc.  cit.  and  Compt.  rend.  76  (1873),  749. 
108Cahours,  loc.  cit.  and  Compt.  rend.  76  (1873),  1383. 


ALKYL  MERCURY 


101 


Other  propyl  mercuric  salts. 

The  cyanide  is  obtained  as  an  oily  product  from  the  action  of 
hydrocyanic  acid  on  the  hydroxide.  It  has  not  been  obtained  pure. 
The  sulfate  is  obtained  as  a  white  crystalline  substance  by  treating 
the  base  with  dilute  sulfuric  acid  or  the  dialkyl  compound  with  con- 
centrated sulfuric  acid.  The  nitrate  is  a  crystalline  substance  prepared 
in  the  same  ways  as  the  sulfate.  The  ar 'senate  is  obtained  as  a  white 
precipitate  on  mixing  solutions  of  the  base  and  arsenic  acid.  The 
oxalate  and  tartrate  are  obtained  in  the  same  way.  The  acetate  is 
made  by  heating  mercury  dipropyl  on  the  steam  bath  with  acetic  acid 
and  diluting  the  resulting  solution  with  water.  The  other  product  of 
the  reaction  is  propane. 

Isopropyl  Mercury  Compounds. 

Isopropyl  mercury  compounds  have  not  been  made  by  any  of  the 
usual  methods  for  making  alkyl  mercury  compounds.  The  electrolytic 
reduction  of  acetone  in  sulfuric  acid  with  a  mercury  cathode  gives 
as  a  by-product  a  volatile  mercury  compound  which  is  probably  mer- 
cury di-isopropyl.109 

Mercury  Isobutyl  Compounds. 

Mercury  Di-isobutyl.110 
Preparation. 

Five  parts  of  isobutyl  iodide  and  one  part  of  pure  ethyl  acetate 
are  shaken  with  twice  the  calculated  amount  of  dilute  sodium  amalgam 
(1  :  400)  in  a  large  separatory  funnel.  The  reaction  takes  place  with 
the  evolution  of  heat.  After  shaking  about  one  hour  heat  is  no  longer 
evolved  and  water  and  ether  are  added  to  the  mixture.  The  ether 
layer  is  separated  and  distilled  on  the  water  bath  and  then  at  a  higher 
temperature.  Steam  distillation  gives  three  layers,  hydrocarbon,  water, 
and  mercury  alkyl.  No  unchanged  iodide  is  left.  The  products  are 
di-isobutyl  and  the  mercury  compound.  These  are  separated  by  frac- 
tional distillation  under  a  pressure  of  70  mm.,  the  hydrocarbon  boil- 
ing at  100°  and  the  mercury  alkyl  at  140°. 

1(>»Tafel,  Ber.  39  (1906),  3626. 

11()Cahours,  Compt.  rend.  77  (1873),  1405.  J.  prakt.  Chem.  (2)  8  (1873),  397. 
Marquardt,  Ber.  21  (1888),  2038. 


102  COMPOUNDS  OF  MERCURY 

Another  method  of  preparation  is  to  use  2  per  cent  sodium  amalgam 
and  add  iodide  and  amalgam  gradually.  The  mixture  is  treated  with 
water  and  the  insoluble  liquid  is  fractionated,  the  mercury  compound 
boiling  at  205-7°  under  atmospheric  pressure. 

Properties. 

Mercury  di-isobutyl  is  a  colorless  liquid  which  is  almost  odorless 
cold  but  has  a  strong  odor  when  hot.  It  is  only  very  slightly  soluble 
in  water  but  soluble  in  alcohol  and  ether.  B.P.  205-7°,  at  70  mm.  140°. 
Its  density  at  15°  is  1.835.  It  is  volatile  with  steam. 

Reactions. 

1.  With  halogens.111 

Iodine  and  bromine  readily  form  isobutyl  halides  and  the  corre- 
sponding alkyl  mercuric  halides. 

2.  With  metals. 

Zinc  and  aluminum  heated  with  the  mercury  dialkyl  in  sealed  tubes 
at  130°  give  isobutyl  compounds  of  the  metals. 

Isobutyl  mercuric  hydroxide. 

The  iodide  reacts  with  moist  silver  oxide  giving  a  strongly  basic 
solution  which  reacts  with  acids  giving  salts  of  mercury  di-isobutyl. 

Isobutyl  mercuric  iodide. 

Mercury  di-isobutyl  reacts  with  iodine  forming  this  compound  and 
isobutyl  iodide.  It  is  a  crystalline  solid. 

Secondary-butyl  Mercury  Compounds. 

Mercury  Di- sec-butyl.112 

This  substance  is  prepared  by  electrolytic  reduction  of  methyl  ethyl 
ketone  in  sulfuric  acid  using  a  mercury  cathode.  The  anode  liquid 
is  20  per  cent  sulfuric  acid  while  the  cathode  liquid  is  30  per  cent. 
The  temperature  is  kept  at  45°  as  lower  temperatures  give  simple  re- 
duction as  the  chief  process.  A  current  of  25  amperes  per  square  deci- 
meter is  passed  at  7  or  8  volts.  In  one  and  a  half  hours  30  gm.  of 
the  ketone  gives  about  40  gm.  of  an  oil  which  is  separated,  washed, 
dried  with  sodium  sulfate,  and  vacuum  distilled  below  80°.  The  boil- 

111  Cahours,  loc.  cit. 

11JTafel,  Ber.  39   (1906),  3628. 


ALKYL  MERCURY  COMPOUNDS  103 

ing  point  at  0.3  mm.  is  46°.  Only  about  30  per  cent  of  pure  product  is 
obtained  from  the  crude  oil.  An  unstable  yellow  residue  remains 
after  the  distillation.  The  mercury  alkyl  cannot  be  distilled  at  ordi- 
nary pressure.  At  15  mm.  it  boils  at  91-93°  (CHHg). 

An  ether  solution  of  mercury  di-sec-butyl  reacts  with  iodine  form- 
ing sec-butyl  iodide  and  a  white  crystalline  compound  which  is  prob- 
ably sec-butyl  mercuric  iodide  as  it  reacts  with  more  iodine  giving 
the  alkyl  iodide. 

Isoamyl  Mercury  Compounds. 

Mercury  di-isoamyl.™ 
Preparation. 

Five  parts  of  isoamyl  iodide  and  one  part  of  ethyl  acetate  are 
shaken  with  dilute  sodium  amalgam.  A  lively  reaction  ensues.  It  is 
necessary  to  cool  the  mixture  from  time  to  time.  When  heat  is  no 
longer  evolved  the  ethyl  acetate  is  distilled  off  on  the  steam  bath. 
Steam  is  then  passed  through  the  mixture  until  about  one-half  of  the 
oily  residue  has  passed  over.  The  residue  is  washed  with  water,  dried 
with  calcium  chloride  and  analyzed. 

Properties. 

Mercury  di-isoamyl  is  a  colorless  transparent  mobile  liquid  of 
faint  amyl  odor.  It  cannot  be  distilled  with  ah  ordinary  vacuum 
apparatus.  If  heated  above  140°  it  decomposes.  It  is  only  slightly 
volatile  with  steam.  It  is  insoluble  in  water,  slightly  soluble  in 
alcohol,  and  readily  soluble  in  ether.  Sp.  g.  at  0°  is  1.666.  (CHHg). 

Reactions. 

1.  With  halogens. 

When  a  little  of  the  mercury  alkyl  is  dropped  into  chlorine  it  gives 
white  fumes  of  isoamyl  mercuric  chloride.  Solid  iodine  dropped  into 
the  liquid  reacts  with  a  hissing  sound.  Bromine  acts  less  violently. 
An  ether  solution  reacts  with  iodine  forming  isoamyl  iodide  and  isoamyl 
mercuric  iodide. 

2.  With  metals. 

Sodium  reacts  forming  sodium  isoamyl.    If  the  reaction  is  carried 

«» Frankland  and  Duppa,  Ann.  130  (1864),  110.  J.  Chem.  Soc.  16  (1863),  420. 
Marquardt,  Ber.  21  (1888),  2038.  L.  W.  Jones,  J.  Am.  Chem.  Boc.  40  (1918),  1269. 
Chem.  Abst.  12  (1918),  2320. 


104  COMPOUNDS  OF  MERCURY 

out  in  ether  and  carbon  dioxide  is  passed  through  the  mixture  isobutyl 
acetic  acid  is  formed.114 

Zinc  heated  with  the  mercury  compound  for  36  hours  in  a  sealed 
tube  at  130°  gives  zinc  di-isoamyl.115 
'  3.  With  acids.118 

Mercury  di-isoamyl  heated  with  glacial  acetic  acid  at  190°  for  16 
hours  gives  isopentane,  metallic  mercury,  and  an  amount  of  amyl  ace- 
tate corresponding  to  one-quarter  of  the  amyl  originally  present. 

4.  With  mercuric  salts. 

The  mercury  compound  treated  with  alcoholic  mercuric  chloride 
gives  isoamyl  mercuric  chloride. 

Isoamyl  mercuric  chloride. 

The  only  preparation  used  is  that  just  mentioned.  It  crystallizes 
in  white  hairlike  needles  from  hot  alcohol.  It  is  insoluble  in  water 
but  very  soluble  in  hot  alcohol  and  ether.  M.P.  86°.  It  sublimes 
on  gentle  heating.  The  best  method  of  purifying  the  substance  is  by 
dissolving  it  in  hot  alcohol  and  precipitating  it  by  adding  water.  In 
this  way  the  last  traces  of  mercuric  chloride  are  removed  more  com- 
pletely than  by  simple  recrystallization  from  alcohol.  (Cl.) 

Isoamyl  mercuric  iodide. 

Very  small  amounts  of  this  substance  are  obtained  by  the  action  of 
metallic  mercury  on  isoamyl  iodide  in  sunlight.117 

The  iodide  has  been  prepared  from  the  dialkyl  compound  and  iodine 
in  ether  solution.  The  first  crystals  obtained  are  washed  with  dilute 
alcohol  and  dried  between  filter  papers.  Recrystallization  from  hot 
alcohol  gives  small  pearly  leaflets.  If  the  alcohol  used  for  recrystal- 
lization contains  a  few  drops  of  alcoholic  potassium  hydroxide  the 
crystallization  is  much  delayed  and  the  substance  separates  in  large 
tablets.  It  is  slightly  soluble  in  boiling  water.  Cooling  the  hot  aque- 
ous solution  gives  fine  crystals.  It  is  readily  soluble  in  ether.  M.P. 
122°.  When  heated  to  140°  the  melted  substance  turns  yellow  and 
some  mercuric  iodide  begins  to  separate.  It  can  be  sublimed  in  a 
stream  of  hot  air.  (CHIHg.) 

"*Schorigin,  Ber.  41   (1908),  2722;  43   (1910),  1937. 

116  Frankland  and  Duppa,  loc.  cit. 
118  L.  W.  Jones,  loc.  cit.  1269. 

117  Frankland  and  Duppa,  loc.  cit.     Frankland,  Ann.  85  (1853),  364. 


ALKYL  MERCURY  COMPOUNDS  105 

n-Octyl  Mercury  Compounds. 

Mercury  Dioctyl.118 
Preparation  and  properties. 

n-Octyl  iodide  is  treated  with  a  very  dilute  sodium  amalgam  until 
no  more  heat  is  evolved.  The  mixture  is  extracted  with  ether  and 
the  ether  is  evaporated  leaving  an  oil  of  very  penetrating  odor.  This 
product  cannot  be  distilled.  At  200°  it  gives  metallic  mercury  and 
dioctyl.  Its  density  at  17°  is  1.342.  The  product  as  obtained  is  nearly 
pure.  (CHHg.)  It  is  insoluble  in  water,  easily  soluble  in  alcohol, 
ether,  and  benzene. 

Reactions. 

1.  With  halogens. 

It  reacts  with  alcoholic  iodine  forming  octyl  mercuric  iodide. 

2.  With  mercuric  salts.    With  alcoholic  mercuric  chloride  it  gives 
octyl  mercuric  chloride. 

Octyl  mercuric  hydroxide. 

The  chloride  in  hot  alcohol  is  treated  with  moist  silver  oxide.  After 
standing  for  five  hours  the  mixture  is  filtered  hot.  On  cooling  the 
filtrate  deposits  yellow  leaflets.  M.P.  75°.  The  product  is  a  strong 
base.  It  is  insoluble  in  cold  water,  slightly  soluble  in  hot,  and  very 
easily  soluble  in  alcohol.  It  liberates  ammonia  from  ammonium  salts 
and  precipitates"  hydroxides  from  solutions  of  salts  of  iron,  aluminum, 
zinc,  and  copper.  (CHHg). 

Octyl  mercuric  chloride. 

The  product  from  mercury  dialkyl  and  mercuric  chloride  gives 
white  crystals  from  alcohol.  (ClHg). 

Octyl  mercuric  iodide. 

Alcoholic  mercuric  iodide  and  the  mercury  dialkyl  give  a  silvery 
white  precipitate  which  is  easily  soluble  in  hot  alcohol.  (IHg). 

Mercury  Compounds  from  Methylene  Iodide. 

Methylene  iodide  reacts  with  metallic  mercury  forming  compounds 
containing  one  or  two  atoms  of  mercury  depending  on  the  amount  of 
the  metal  used. 

118Eichler,  Ber.  12   (1879),  1880. 


106  COMPOUNDS  OF  MERCURY 

lodomethyl  mercuric  iodide,  I  —  CH2  —  Hgl.119 

Methylene  iodide  reacts  with  the  Calculated  amount  of  mercury  in 
sunlight  forming  the  mono-mercury  compound  and  a  small  amount 
of  an  extremely  insoluble  tri-mercurated  compound  which  is  due  to 
an  impurity  of  iodoform  in  the  methylene  iodide  used.  The  reaction 
takes  place  more  rapidly  if  the  halide  contains  a  trace  of  iodine  or 
mercurous  iodide.  The  mono-mercury  compound  is  soluble  only  in 
hot  methylene  iodide.  M.P.  109°.  Refluxing  with  alcoholic  mercuric 
chloride  replaces  the  iodine  attached  to  carbon  by  chlorine  forming 
chloromethyl  mercuric  iodide,  Cl  —  CH^  — Hgl.  Treatment  with 
bases  gives  metallic  mercury  at  once.  Treatment  with  hydrochloric 
acid  or  with  potassium  iodide  solution  gives  methyl  mercuric  iodide. 
No  explanation  of  this  unusual  reaction  is  known. 

Methylene  di-mercuric  iodide,  CH2(HgI)2. 

It  is  prepared  like  the  preceding  compound  but  by  using  an  excess 
of  mercury.  Its  properties  are  like  those  of  the  mono-mercury  com- 
pound but  it  is  even  less  soluble.  Treatment  with  hydrochloric  acid 
gives  inorganic  mercury  and  methyl  mercuric  iodide.  The  substance 
reacts  with  ethyl  iodide  but  the  products  have  not  been  identified 

Methine  tri-mercuric  iodide,  CH(HgI)3. 

This  substance  is  obtained  as  a  by-product  in  the  preparation  of 
the  above  substances  from  methylene  iodide  containing  a  little  iodo- 
form. It  is  insoluble  in  all  solvents  even  hot  methylene  iodide.  It 
reacts  with  iodine  giving  iodoform. 

"•Sakurai,  J.  Chem.  Soc.  37   (1880),  658 ;  39   (1881),  485;  41   (1882),  360. 


Chapter  V. 
Mercury  Compounds  Obtained  from  the  Olefines. 

Mercury  Compounds  of  Ethylene.1 

Ethylene  reacts  with  aqueous  solutions  of  mercuric  salts  giving 
various  complicated  mercury  compounds.  From  these  have  been  ob- 
tained two  types  of  simpler  mercury  compounds,  ethanol  mercuric 
salts  and  diethyl  ether  mercuric  salts,  CH2OH  —  CH2  —  HgX  and 
0  (CH2  —  CH2  —  HgX)  2  respectively.  Substances  believed  to  be  vinyl 
mercury  compounds  of  the  formula  CH2  =  CH  —  HgX  have  since 
been  found  to  be  ethanol  mercuric  salts. 

If  the  reaction  between  ethylene  and  mercuric  salts  is  carried 
out  in  alcohol  instead  of  in  water  it  takes  place  more  rapidly. 
The  product  corresponds  to  the  ethanol  mercuric  salts  but  has  an 
alkoxyl  group  instead  of  the  hydroxyl  of  the.  latter  compounds, 
RO  — CH2  — CH2  — HgX. 

The  original  workers  with  these  substances  expressed  the  opinion 
that  there  might  be  two  forms  of  the  ethanol  mercuric  salts,  1 — that 
indicated,  and  2 — an  intermediate  addition  product  of  a  molecule  of 
ethylene  and  a  molecule  of  a  basic  mercuric  salt,  C2H4.Hg(OH)X. 
Later  investigators  go  farther  and  claim  that  all  of  these  ethylene 
mercury  compounds  are  merely  molecular  addition  compounds  and  do 
not  correspond  to  any  structural  formulas.2  The  three  types  of  prod- 
ucts would  then  be  represented  by  the  formulas 

"Ethanol  mercuric  salts,"  C2H4.Hg(OH)X 

"Ethyl  ether  mercuric  salts,"  2C2H4.HgO.HgX2 

Product  from  reaction  in  alcohol,  ROH,        C2H4.Hg(OR)X. 

Neither  the  "structure"  formulas  nor  the  "addition"  formulas  are  en- 
tirely satisfactory.  The  original  conception  of  the  compounds  as 
true  C  —  Hg  compounds  does  not  explain  the  fact  that  all  three  of 

iHofmann  and  Sand,  Ber.  33  (1900),  1340,  2692.  Biilmann,  Ber.  33  (1900),  1641. 
Sand,  Ber.  34  (1901),  1385,  2906.  Sand  and  Singer,  Ber.  35  (1902),  3170.  Sand  and 
Breest,  Z.  physik.  Ghent.  59  (1907),  424. 

2Manchot,  Ber.  53  (1920),  984. 

107 


108  COMPOUNDS  OF  MERCURY 

these  substances  react  with  dilute  halogen  acids  giving  quantitative 
yields  of  ethylene.  The  "addition"  formulas  explain  the  ready  forma- 
tion of  ethylene  by  treatment  with  acids  and.  alkyl  halides  but  give  no 
explanation  of  the  fact  that  the  compounds  of  this  kind  under  proper 
conditions  give  ethyl  alcohol,  ethylene  iodhydrine,  and  (3(3'-di-iododi- 
ethyl  ether. 

Complex  compounds  obtained  from  ethylene  and  mercuric  salts. 

A  compound,  C6#1004C74#04,  is  obtained  as  a  white  precipitate  by 
passing  ethylene  into  an  aqueous  solution  not  quite  saturated  with 
mercuric  chloride.  It  forms  thin  shining  doubly  refractive  plates.  On 
standing  about  twelve  hours  larger  crystals  separate  which  can  easily 
be  removed  leaving  the  fine  plates  which  are  the  desired  substance. 
The  larger  crystals  consist  of  a  double  salt  of  mercuric  chloride  and 
ethanol  mercuric  chloride.  The  fine  crystals  are  almost  insoluble  in 
hot  alcohol.  (CHClHg) .  Warming  with  acid  gives  ethylene  quantita- 
tively. The  compound,  HgCl2.(CH2OH  —  CH2HgCl),  consists  of  the 
larger  crystals  as  just  described.  (CHClHg).  It  is  soluble  in  a  large 
amount  of  water.  It  can  be  recrystallized  from  methyl  or  ethyl  alco- 
hol. Bases  precipitate  only  one-half  of  the  mercury  as  the  oxide.  Hy- 
drogen sulfide  slowly  precipitates  all  of  the  mercury  as  mercuric  sul- 
fide.  The  filtrate  from  the  mercuric  sulfide  contains  alcohol.  This 
fact  seems  to  favor  the  conception  that  the  ethanol  mercury  com- 
pound is  in  reality  a  mercurated  ethyl  alcohol.  Potassium  cyanide 
or  acids  give  ethylene  with  the  mercury  compound.  The  compound, 
C6H1004Hg4(SOJ2)  is  precipitated  by  passing  ethylene  into  an  almost 
neutral  mercuric  sulfate  solution.  (CHSHg).  When  heated  with  acids 
it  gives  a  quantitative  yield  of  ethylene.  This  substance  has  been 
claimed  to  be  ethanol  mercuric  sulfate  (CH2OH  — CH2  — Hg)2SO4 
but  the  evidence  appears  to  favor  the  more  complex  formula. 

Ethanol  mercuric  chloride,  CH2OH  —  CH2  —  HgCl. 

Mercuric  nitrate  solution  is  treated  with  potassium  hydroxide  solu- 
tion until  a  slight  precipitate  of  the  basic  salt  persists  after  shaking. 
Ethylene  is  passed  in  to  dissolve  the  precipitate.  More  alkali  is  added 
and  then  more  ethylene.  This  is  kept  up  until  no  more  ethylene  is 
absorbed.  The  filtered  solution  is  then  treated  with  the  calculated 
amount  of  potassium  chloride  and  allowed  to  stand  for  a  few  hours. 
Carbon  dioxide  is  then  passed  in  to  precipitate  the  chloride  from  its 


OBTAINED  FROM  THE  OLEFINES  109 

alkaline  solution.  The  mother  liquor  is  evaported  to  dryness  and 
extracted  with  methyl  alcohol  to  recover  the  last  of  the  chloride.  It 
is  recrystallized  from  methyl  alcohol.  (CHHg).  M.P.  155°.  Hydro- 
chloric acid  gives  ethylene.  The  solubility  of  the  chloride  at  25°  is 
about  .01  mole  per  liter  of  water.  The  change  in  its  conductivity  with 
dilution  indicates  considerable  hydrolysis.3 

Ethanol  mercuric  bromide. 

Its  preparation  is  like  that  of  the  chloride  just  described.  It  also 
is  recrystallized  from  methyl  alcohol.  (CHBrHg).  It  is  soluble  in  20.5 
parts  of  alcohol  at  22°  and  in  3.33  parts  at  80°.  It  gives  ethylene 
with  20  per  cent  hydrochloric  acid  at  15°.  It  reacts  very  slowly  with 
30  per  cent  acetic  acid  in  the  cold  but  gives  ethylene  rapidly  on  heat- 
ing. Cold  bases  dissolve  the  bromide  giving  a  clear  solution.  Am- 
monium sulfide  gives  a  white  precipitate. 

An  alkaline  solution  of  sodium  stannite  gives  mercury  and  a  poison- 
ous volatile  mercury  compound  having  a  strong  smell  like  carbylamine. 
This  substance  may  be  Hg(CH2  —  CH2OH)2. 

An  alcoholic  solution  of  the  bromide  treated  with  bromine  and  po- 
tassium hydroxide  gives  a  white  crystalline  substance  which  analyzes 
for  a  mercurated  acetic  acid,  BrHg  —  CH2  —  C02H. 

The  bromide  dissolved  in  absolute  alcohol  reacts  with  dry  ammonia 
giving  a  white  crystalline  precipitate  of  CH2OH  —  CH2HgBr.NH3. 
(NH3).  M.P.  150°. 

A  solution  of  the  bromide  in  the  least  possible  amount  of  boiling 
alcohol  deposits  fine  crystals  on  cooling.  When  the  cold  mixture  is 
treated  with  sodium  ethylate  solution  the  crystals  dissolve.  After  a 
few  minutes  a  thick  white  powder  separates.  This  is  washed  with 
hot  absolute  alcohol.  M.P.  146°,  not  sharp.  It  is  soluble  in  cold 
water  giving  an  alkaline  solution.  Small  amounts  of  dilute  acids  give 
white  precipitates  which  dissolve  in  an  excess  of  acid  forming  ethylene. 
This  substance  may  be  the  anhydride  of  p-hydroxymercuri-ethyl  alco- 

CH2  — Hg. 

hoi,    |  | 

CH2  — O 

Ethanol  mercuric  iodide. 

Its  preparation  is  like  that  of  the  chloride  and  bromide.  (Hg) .  M.P. 
147°.  Hydrochloric  acid  gives  ethylene.  Reduction  in  alkaline  solu- 

«Sand  and  Breest,  Z.  physik.  Chem.  59  (1907),  424, 


110  COMPOUNDS  OF  MERCURY 

tion  by  electrolysis  or  by  sodium  amalgam  gives  ethyl  alcohol  which 
is  identified  by  transforming  it  to  iodoform  and  to  silver  acetate.4  It  is 
easily  soluble  in  one  molecule  of  alkali.  It  also  dissolves  in  alcoholic 
sodium  ethylate.  When  this  solution  is  treated  with  methyl  iodide  and 
refluxed  the  original  iodide  is  recovered  unchanged.  The  iodide  reacts 
with  iodine  giving  ethylene  iodhydrine.  Heating  the  iodide  with 
methyl  iodide  gives  mercuric  iodide,  ethylene,  and  methyl  alcohol. 
Heating  with  mercuric  oxide  and  potassium  hydroxide  gives  mercuri- 
hydroxymercuri-acetic  acid,  Hg  =  C  —  C02H.  5 

HgOH 

Ethanol  mercuric  nitrate. 

It  is  prepared  from  the  chloride  and  silver  nitrate  in  methyl  alcohol. 
The  filtrate  is  evaporated  over  sulfuric  acid.  (NHg) .  When  heated  it 
decomposes  with  a  slight  puff  and  the  formation  of  red  vapors.  Hy- 
drochloric acid  precipitates  the  chloride.  An  excess  of  acid  must  be 
avoided  as  it  liberates  ethylene.  Potassium  cyanide  solution  also  gives 
ethylene.  Oxygen  acids  give  this  reaction  only  very  slightly. 

Ethanol  mercuric  sulfide.     (CH2OH  —  CH2  —  Hg  — )  2S. 

An  alkaline  solution  of  the  chloride  is  treated  with  potassium  sul- 
fide. A  pure  white  precipitate  is  obtained  (CHSHg) .  Boiling  the  sul- 
fide with  water  gives  a  solution  which  on  cooling  deposits  crystals  of 
ethanol  mercuric  sulfhydrate  which  can  be  recrystallized  from  wa- 
ter. (CHSHg). 

Benzoate  of  ethanol  mercuric  iodide,  C6H5CO — 0 — CH2 — CH2 — Hgl. 6 
A  solution  of  the  iodide  in  10  per  cent  potassium  hydroxide  is 
treated  with  benzoyl  chloride.  The  white  precipitate  obtained  is 
purified  by  dissolving  in  alcohol  and  precipitating  by  water  and  po- 
tassium iodide  solution.  It  can  be  recrystallized  from  alcohol.  (CHHg) . 
M.P.  118°.  It  is  easily  soluble  in  organic  solvents  but  is  insoluble  in 
water  and  in  alkalies.  Fuming  hydrochloric  acid  gives  ethylene  slowly. 
This  inactivity  may  be  due  to  the  extreme  insolubility  of  the  substance 

I 
/ 
in  water.  Manchot  formulates  this  substance  as  C2H4.Hg 

0  —  COCCH5 

4  Sand  and  Singer,  Ber.  35  (1902),  3180. 

•Hofmann  and  Sand,  Ber.  34  (1901),  1385,  2906. 

'Sand,  Ber.  34  (1901),  1390.    Manchot,  Ber.  53  (1920),  984. 


OBTAINED  FROM  THE  OLEFINES  111 

Treatment  of  ethanol  mercuric  bromide  with  acetic  anhydride  does  not 
give  an  acetyl  derivative.  The  compound  obtained  is  described  as  a 
"mono-mercury  acetic  acid"  and  has  the  formula  C2H302BrHg. 
(CHHg).  However,  its  sharp  melting  point  of  117-18°  marks  it  as 
being  different  from  the  known  bromomercuri  acetic  acid.  It  may  be 

Br 
/ 

a  "mixed"  salt  of  mercury,  Hg 

\ 

0  — COCH3 
W-Di-chloromercuri  diethyl  ether,  0(CH2  — CH2  — HgCl)2.7 

A  practically  neutral  solution  of  mercuric  sulfate  is  obtained  by 
dissolving  yellow  mercuric  oxide  in  30  per  cent  sulfuric  acid,  adding 
more  of  the  oxide  until  some  insoluble  basic  salt  is  formed,  and  then 
filtering  the  solution.  The  solution  is  treated  with  ethylene.  A  white 
precipitate  forms  almost  at  once.  After  about  8  hours  the  precipitate 
is  filtered,  washed,  and  treated  with  15  per  cent  potassium  hydroxide 
which  dissolves  all  but  a  slight  black  residue.  The  filtered  alkaline 
solution  is  treated  with  potassium  chloride  and  saturated  with  carbon 
dioxide.  The  chloride  separates  as  a  white  crystalline  precipitate.  It 
is  difficultly  soluble  in  water,  alcohol,  and  ether.  M.P.  190°,  not  sharp. 
(CHClHg). 

The  chloride  can  also  be  obtained  from  the  complex  precipitate 
formed  from  ethylene  and  mercuric  chloride.  It  does  not  react  as 
Veadily  with  acids  as  does  the  corresponding  ethanol  mercury  com- 
pound. It  does  however  form  ethylene  slowly.  This  slowness  of  re- 
action may  be  due  to  its  slight  solubility  in  aqueous  reagents. 

The  corresponding  bromide  is  made  in  the  same  way  as  the  chloride. 
It  forms  a  fine  white  powder  which  is  almost  insoluble  in  water,  alco- 
hol, and  ether.  At  24°  it  dissolves  in  6595  parts  of  absolute  alcohol. 
It  sinters  about  200°  (CHHg).  It  reacts  slowly  with  acids  giving 
ethylene.  It  dissolves  in  sodium  hydroxide  giving  a  clear  solution. 

The  iodide  is  prepared  in  the  same  way  as  the  other  halides  except 
that  it  precipitates  from  the  cold  alkaline  solution  without  the  use  of 
carbon  dioxide.  It  is  purified  by  recrystallization  from  15  per  cent  po- 
tassium hydroxide.  M.P.  161°.  Treatment  of  the  iodide  with  iodine  in 
potassium  iodide  gives  a  90  per  cent  yield  of  (3(3'-di-iododiethyl  ether. 
This  is  obtained  by  steam  distillation  as  a  colorless  oil.  (CHI).  Its 
structure  is  proved  by  converting  it  to  morpholine, 

.'Sand,  Ber.  34  (1901),  2907. 


112  COMPOUNDS  OF  MERCURY 

CH2  —  CH2 

/  \ 

0  NH. 

\  / 

CH2  —  CH2 

This  is  done  by  heating  the  di-iodide  with  toluene  sulfonamide  and  de- 
composing the  resulting  compound  with  hydrochloric  acid  at  170°.  The 
morpholine  hydrochloride  obtained  melts  175-6°.  It  is  further  identi- 
fied by  changing  it  to  the  picrate  and  the  chloroplatinate.  The  di- 
iododiethyl  ether  also  gives  a  monoquinoline  salt  melting  at  176° 
(CHI),  and  a  diquinoline  salt  melting  with  decomposition  at  254°  (I). 
The  corresponding  carbonate  0  (CH2  —  CH2  —  Hg  — )  2C03,  is  ob- 
tained by  passing  carbon  dioxide  directly  into  the  alkaline  solution  of 
the  product  obtained  from  ethylene  and  mercuric  sulfate.  It  is  a 
white  solid  soluble  in  alkalies.  (CH,C03,Hg). 

Cyclic  mercury  compounds  obtained  from  the  diethyl  ether  di-mercuric 
halides.8 

Treatment  of  the  halides  with  an  alkaline  sodium  stannite  solu- 
tion gives  a  gray  violet  precipitate  of  an  organic  mercurows  compound, 

CH2  — CH2  — Hg 


O 


which  is  fairly  stable  as  it  requires  a  tern- 


CH2-CH2-Hg 
perature  of  140°  to  change  it  to  metallic  mercury  and  the  correspond- 

CH2  — CH2 
/  \ 

ing  mercuric  compound,  0  Hg. 

\  / 

CH2  — CH2 

Mercurous  diethylene  oxide,  0  =  (CH2  —  CH2)2  =  Hg2. 

It  is  prepared  as  just  mentioned  by  adding  a  filtered  sodium  stan- 
nite solution  to  an  alkaline  solution  of  diethyl  ether  di-mercuric  bro- 
mide or  the  original  precipitate  from  ethylene  and  the  barely  acid 
solution  of  mercuric  sulfate.  The  product  forms  as  a  gray  violet  pre- 
cipitate in  almost  quantitative  yield.  It  sinters  about  80°  and  melts 
140-150°.  (CHHg).  When  dry  it  forms  a  gray  black  powder  insoluble 
in  water,  alkalies,  and  organic  solvents.  Heated  in  a  tube  with  dry 

Ber.  34  (1901),  2913. 


OBTAINED  FROM  THE  OLEFINES  113 

ether  or  benzene  for  a  few  hours  at  140°  it  gives  mercury  and  crys- 
tals of  the  mercuric  compound. 

Mercuric  diethylene  oxide,  0  =  (CH2  —  CH2)2  =  Hg. 

It  is  prepared  from  the  mercurous  compound  as  just  described. 
It  forms  long  thin  colorless  prisms  from  benzene.  Yield  60  per  cent. 
M.P.  145°.  (CHHg).  It  has  a  peculiar  odor.  It  is  insoluble  in  water, 
alkalies,  and  dilute  mineral  acids,  but  easily  soluble  in  warm  benzene, 
toluene  and  alcohol.  It  is  difficultly  soluble  in  ether  and  very  diffi- 
cultly soluble  in  acetone.  Potassium  hydroxide,  potassium  iodide,  and 
potassium  cyanide  give  no  action  even  on  long  boiling.  This  stabil- 
ity to  potassium  cyanide  is  in  sharp  contrast  to  the  easy  formation  of 
ethylene  from  the  ethanol  mercury  compounds.  However,  fuming 
hydrochloric  acid  gives  ethylene  and  mercuric  chloride. 

A  benzene  solution  reacts  with  an  ether  solution  of  picric  acid  giv- 
ing a  crystalline  picrate.  (CHN) .  Its  formation  is  probably  due  to  the 
oxygen  in  the  six  membered  ring. 

A  cold  benzene  solution  reacts  with  an  ether  solution  of  mercuric 
chloride  formmg  a  precipitate  containing  two  molecules  of  mercuric 
chloride.  (CH) .  This  substance  is  formulated  as  an  addition  product, 
0  =  (CH2  — CH2)2  =  Hg.2HgCl2.  It  may  be  that  one  molecule  of 
the  mercuric  chloride  acts  as  mercuric  salts  always  do  with 
C  —  Hg  —  C  compounds  forming  (3|3'-di-chloromercuri  diethyl  ether. 
The  other  molecule  of  mercuric  chloride  would  then  be  more  loosely 
combined.9  In  fact  sodium  hydroxide  is  said  to  precipitate  "some"  of 
the  mercury  in  the  compound  as  the  oxide.  A  quantitative  determi- 
nation of  the  fraction  of  the  mercury  precipitated  in  this  way  would 
decide  which  of  these  explanations  is  correct. 

Products  Obtained  from  Ethylene  and  Mercuric  Salts  in  Alcohol.10 

Ethylene  is  absorbed  much  more  rapidly  by  a  solution  of  mercuric 
acetate  in  methyl  alcohol  than  by  an  aqueous  solution.  The  product 
is  formed  by  the  addition  of  the  groups  — HgOAc  and  —  OCH3  to 
the  ethylene  double  bond.  When  other  alcohols  are  used  the  corre- 
sponding alkoxyl  group  appears  in  the  product.  If  the  product  is  not 
regarded  as  a  "structural"  compound  it  may  be  formulated  as 

8  Stoehr,  J.  prakt.  Chem.  (2)  55  (1897),  80. 

and  Schrauth,  B&r.  46  (1913),  2867.    Manehot,  Ber.  53  (1920),  986. 


114  COMPOUNDS  OF  MERCURY 

OAc 

C2H,.Hg 

\ 
OCH3 

a-Acetoxymercuri-fi-methoxy  ethane,  AcOHg  —  CH2  —  CH2  —  OCH3. 

Ethylene  free  from  air  is  passed  into  mercuric  acetate  in  methyl 
alcohol  in  a  special  shaking  apparatus.  In  one  hour  almost  exactly 
one  mole  of  ethylene  is  absorbed  and  all  of  the  acetate  is  dissolved. 
Most  of  the  alcohol  and  the  acetic  acid  formed  in  the  reaction  are 
removed  by  distillation  under  diminished  pressure.  The  oily  residue 
solidifies  on  standing.  It  is  recrystallized  from  low  boiling  ligroin. 
Yield  82  per  cent.  M.P.  42°.  (CHHg).  It  is  very  soluble  in  water 
and  common  solvents.  It  gives  bad  blisters  on  the  skin.  A  water 
solution  treated  with  a  little  hydrochloric  acid  gives  a  precipitate  of 
the  corresponding  chloride.  An  excess  of  acid  gives  ethylene  on  warm- 
ing. Alkalies  and  carbonates  give  no  visible  change.  Ammonium  sul- 
fide  in  the  cold  gives  a  white  amorphous  precipitate  which  blackens 
slowly  in  the  cold  but  rapidly  on  heating.  Sodium  stannite  solution 
gives  metallic  mercury  even  in  the  cold.  At  first  a  slight  violet  color 
appears.  This  may  indicate  the  formation  of  an  unstable  mercurous 
compound.  No  product  except  the  mercury  is  mentioned.  The  ace- 
tate decolorizes  permanganate  and  iodine  solutions. 

The  corresponding  bromide  is  obtained  from  an  alcoholic  solution 
of  the  acetate  and  an  aqueous  solution  of  potassium  bromide.  It  forms 
white  leaflets  from  dilute  alcohol.  The  solution  of  the  substance  in 
ethyl  acetate  can  be  precipitated  by  low  boiling  ligroin.  M.P.  58° 
(CHBrHg).  It  is  very  readily  soluble  in  organic  solvents  except  low 
boiling  ligroin  (petroleum  ether) .  It  is  rather  difficultly  soluble  in  cold 
water.  The  iodide  is  obtained  in  the  same  way  as  the  bromide.  It 
is  purified  by  dissolving  in  ethyl  acetate  and  precipitating  with  low 
boiling  ligroin.  Its  solubilities  resemble  those  of  the  bromide.  It  is 
not  very  stable.  (CHIHg). 

a-Acetoxymercuri-fi-ethoxy  ethane. 

It  is  prepared  in  the  same  way  as  the  methoxy  compound.  Yield 
95  per  cent.  It  is  very  soluble  in  water  and  organic  solvents  includ- 
ing low  boiling  ligroin.  (CHHg,MW).  On  rapid  heating  it  sinters  at 
33°  and  melts  at  36°.  The  chloride  is  prepared  from  the  acetate  and 


OBTAINED  FROM  THE  OLEFINES  115 

sodium  chloride.  It  is  purified  from  ethyl  acetate  and  low  boiling 
ligroin.  (CHClHg).  M.P.  92°.  It  is  very  soluble  in  alcohol,  chloro- 
form, ethyl  acetate,  and  acetone,  fairly  soluble  in  ether  and  benzene, 
less  soluble  in  water  and  very  difficultly  soluble  in  ligroin,  both  low 
and  high  boiling.  When  the  chloride  is  heated  with  methyl  iodide  at 
100°  mercuric  salts  and  almost  exactly  one  mole  of  ethylene  are  pro- 
duced. The  bromide  and  iodide  are  prepared  in  the  same  way  but 
have  not  been  studied  in  detail. 

Mercury  Compounds  Obtained  from  Propylene.11 

Propylene  reacts  with  mercury  salts  giving  two  types  of  compounds 
corresponding  to  those  obtained  from  fcthylene,  propanol  mercuric 
salts  of  the  formula  CH3  —  CHOH  —  CH2HgX,  and  isopropyl  ether 

CH3 

/ 
mercuric  salts  of  the  formula  0  =  (CH  )2.    In  the  addition 

CH2  — HgX 

to  the  double  bond  the  mercury  adds  to  the  carbon  having  the  most  hy- 
drogen atoms. 

a- Acetoxymercuri-fi-hydroxy  propane,  CHa — CHOH — CH2 — HgOAc. 

A  solution  of  the  substance  is  obtained  from  propylene  and  mercuric 
acetate  solution.  The  pure  substance  has  not  been  isolated.  Treat- 
ment with  potassium  permanganate  solution  does  not  give  the  mer- 
curated  acetone  which  might  be  expected  but  a  more  complex  product 
C6H1205Hg3  which  has  not  been  further  studied.  (CHHg). 

The  corresponding  chloride  is  made  by  treating  basic  mercuric  ni- 
trate with  propylene  and  adding  the  calculated  amount  of  potassium 
chloride.  The  preparation  is  carried  out  in  the  same  way  as  with 
ethylene.  The  chloride  is  so  soluble  that  it  cannot  be  precipitated 
from  the  alkaline  solution  by  carbon  dioxide  but  has  to  be  extracted 
with  ether.  It  is  recrystallized  from  ether.  (CHHg).  M.P.  about  53°. 
The  bromide  is  prepared  in  the  same  way  as  the  chloride.  After  the 
addition  of  the  potassium  bromide  to  the  alkaline  solution  the  mixture 
is  allowed  to  stand  for  12  hours  and  is  then  saturated  with  carbon 
dioxide.  The  precipitate  is  crystallized  from  a  mixture  of  absolute 

"Hofmann  and  Sand,  Ber.  33  (1900),  1354.  Sand  and  Singer,  Ber.  35  (1902), 
3172.  Sa»d  and  Genssler,  Ber.  36  (1903),  3704. 


116  COMPOUNDS  OF  MERCURY 

alcohol  and  ether.  (CH).  M.P.  76°.  The  bromide  cannot  be  oxidized 
to  the  corresponding  mercurated  acetone  but  gives  the  complex  mer- 
cury compound  obtained  from  the  chloride.  The  iodide  is  prepared 
in  the  same  way  as  the  bromide.  It  is  recrystallized  from  benzene 
forming  fine  needles,  (CH,I  high,Hg).  M.P.  68°.  It  is  easily  soluble 
in  absolute  alcohol  and  ether,  difficultly  soluble  in  carbon  disulfide, 
benzene  and  water.  It  reacts  with  hydrochloric  acid  giving  propylene. 

Reduction  of  the  iodide  with  sodium  amalgam  followed  by  acidifi- 
cation with  sulfuric  acid,  treatment  with  silver  nitrate,  filtration,  oxi- 
dation by  potassium  dichromate  and  sulfuric  acid,  distillation  with 
alkali,  and  treatment  with  hydroxylamine  gives  acetone  oxime  melting 
at  60°.  This  shows  that  the  original  substance  was  a  substituted 
isopropyl  alcohol. 

Alkaline  solutions  of  the  propanol  mercuric  halides  react  with  hy- 
drogen sulfide  forming  a  white  precipitate  which  is  soluble  in  excess 
of  sulfide.  The  two  substances  are  probably  the  sulfide  and  the  hy- 
drosulfide  of  the  organomercuric  residue. 

Di-bromomercuri  'di-isopropyl  ether, 

CH3  CH3 

\  / 

CH  — 0  — CH 

/  \ 

BrHg  — CH2  CH2  — HgBr 

It  is  obtained  as  a  small  insoluble  residue  during  the  preparation 
of  the  propanol  compound.  It  is  purified  by  dissolving  in  pure  potas- 
sium hydroxide  and  precipitating  by  carbon  dioxide.  It  is  a  heavy 
crystalline  powder  insoluble  in  all  common  solvents.  (CHHg) .  It  does 
not  melt.  The  corresponding  iodide  is  obtained  from  an  alkaline  solu- 
tion of  the  bromide  and  potassium  iodide.  It  can  be  recrystallized  from 
hot  alkali.  It  is  insoluble  in  all  common  solvents.  (Hg) . 

Mercury  Compounds  from  Isobutylene.13 

A  number  of  complex  mercury  compounds  are  obtainable  from  iso- 
butylene.  One  which  is  obtained  by  means  of  mercuric  nitrate  is  ex- 
plosive on  percussion  or  on  warming  to  80°.  It  is  formulated  as 

"Sand  and  Genssler,  Ber.  36  (1903),  3704. 

13  Denig&s,  Ann,,  ohim.  phys.  (7)  18  (1899),  386.  Hofmann  and  Sand,  Ber.  33 
(1900),  1356. 


OBTAINED  FROM  THE  OLEFINES  117 

(CH3)2  =  C  —  HgN03.  (CHNHg,C4H8) .    Hydrochloric  acid 

CH2-Hg-HgN03 

regenerates  isobutylene  and  forms  a  mixture  of  mercuric  and  mercur- 
ous  chlorides. 

Chloromercuri  hydroxy  isobutane,  (CH3)2  =  C(OH)  — CH2HgCl. 

A  solution  of  the  acetate  or  nitrate  of  mercury  is  treated  with  pure 
alkali  until  a  slight  permanent  precipitate  forms.  The  solution  of  the 
basic  salt  is  then  treated  with  isobutylene  and  alkali  alternately  until 
no  more  butylene  reacts.  The  alkaline  solution  is  treated  with  the 
calculated  amount  of  potassium  chloride  and  allowed  to  stand  for 
12  hours.  It  is  then  saturated  with  carbon  dioxide  and  extracted  with 
ether  as  the  chloride  does  not  precipitate  out.  The  ether  is  evaporated. 
The  residue  is  recrystallized  from  dry  ether.  (CH).  M.P.  52°.  The 
bromide  is  obtained  in  the  same  way  but  forms  a  precipitate  when 
carbon  dioxide  is  passed  through  its  alkaline  solution.  The  precipitate 
is  extracted  with  ether  and  the  product  is  recrystallized  from  benzene. 
(CHBrHg).  Small  shining  prisms.  M.P.  66°.  Hydrochloric  acid 
gives  isobutylene.  It  is  easily  soluble  in  bases.  Hydrogen  sulfide  gives 
a  white  oily  precipitate  which  is  easily  soluble  in  an  excess  of  hydrogen 
suiiicie  water  and  in  alcohol.  The  bromide  dissolved  in  dry  ether  re- 
acts with  ammonia  forming  a  compound  C4H8(OH)HgBr.NH3. 
(CHg,NH3).  The  substance  obtained  in  the  same  way  as  the  chloride 
and  bromide  but  with  the  use  of  potassium  iodide  is  probably  the  cor- 
responding iodide  although  it  appears  in  the  literature  as  C4H7HgI.14 
It  can  be  crystallized  from  dry  ether,  benzene,  or  carbon  disulfide. 

Mercury  Compounds  from  the  Higher  Ethylene  Hydrocarbons. 

Trimethyl  ethylene  (amylene),  sym.  dimethyl  ethylene,  and  di- 
methyl ethyl  ethylene  have  been  treated  with  mercuric  salts.  In  some 
cases  complex  mercury  compounds  are  obtained  and  in  others  the 
mercury  salts  act  merely  as  oxidizing  agents.15 

l4Hofmann  and  Sand,  Ber.  33  (1900),  1358. 

"Hofmann  and  Sand,  Ber.  33  (1900),  1340.  Denigfcs,  Ann.  oMm.  phys.  (7)  18 
(1899),  385.  Bull.  soc.  cMm.  (3)  19  (1898),  494.  Balbiano  and  Paolini,  Ber.  35 
(1902),  2994.  Balbiano,  Oazz.  chim.  ital.  36  I  (1906),  238. 


118  COMPOUNDS  OF  MERCURY 

Mercury  Compounds  from  Acetylenes. 

Acetylene  reacts  with  solutions  of  mercuric  salts  giving  extremely 
insoluble  amorphous  precipitates.  When  these  precipitates  are  treated 
with  mineral  acids  acetalclehyde  is  produced.  This  reaction  first  dis- 
covered by  Kutscheroff  1G  has  become  very  important  as  a  means  of 
producing  ethyl  alcohol  and  acetic  acid  from  acetylene.  The  nature 
of  the  organic  mercury  compounds  first  formed  is  by  no  means  settled 
although  many  chemists  have  proposed  formulas  for  them.17  The 
problem  is  of  theoretical  rather  than  immediate  practical  interest  as 
the  mercurated  products  are  not  isolated  but  are  continuously  changed 
to  acetaldehyde  by  the  acid  present  during  their  formation.  The  role 
of  the  mercury  salts  thus  becomes  that  of  catalysts.  Among  the 
formulas  which  have  been  suggested  for  the  intermediate  mer- 
cury compounds  obtained  from  acetylene  and  mercuric  chloride  are 
Cl  —  CH  =  CH  —  HgCl  and  (ClHg)3C  —  CHO.  Monochloroacetylene 
reacts  with  mercuric  chloride  giving  a  product  which  is  believed  to  be 
trichloromcrcuri-acetic  acid.18  Acetylene  reacting  with  a  slightly  acid 
solution  of  mercuric  nitrate  gives  a  substance  believed  to  have  the 
formula  Hg  =  C  —  CHO.  19 


Other  investigators  interpret  these  products  from  acetylene  as 
"double  compounds"  of  acetylene  or  mercury  acetylide  with  various 
amounts  of  mercuric  salts,  mercuric  or  mercurous  oxide,  and  water. 
Complicated  formulas  are  arrived  at  which  agree  with  the  analytical 
results.  The  chief  difficulty  in  the  study  of  these  compounds  is  their 
extreme  insolubility  which  prevents  their  purification.  Moreover  the 
composition  of  the  precipitates  obtained  undoubtedly  varies  consider- 
ably with  changing  conditions. 

™Ber.  14  (1881),  1540. 

17  Kutscheroff,  loc.  cit.     Plimpton,  Proc.   Chem.   Soc.  8    (1892)    110.     Reiser,  Am. 
Chem.  J.  15   (1893),  537.     Plimpton  and  Travers,  J.  Chem.  Soc.  65   (1894),  266.     Hof- 
mann,   Ber.   31    (1898),    2213,    2783.      Kothner,    Ibid.    2475.      Erdmann    and    Kothner, 
Z.  anorg.  Chem.  18  (1898),  53.     Biginelli,  CJiem.  Zentr.  1898  I  925.     Hofmann,  Ber.  32 

(1899),  874.  LeComte,  J.  pharm.  chim.  (6)  16  (1902),  297.  Chem.  Zentr.  1902  II 
1499.  Burkard  and  Travers,  J.  CJiem.  Soc.  81  (1902),  1270.  Biltz  and  Mumra,  Ber.  37 
(1904),  4417.  Hofmann,  lUd.  4459.  Biltz,  Ber.  38  (1905),  133.  Brame,  J.  Chem. 
Soc.  87  (1905),  427.  Nieuwland  and  Maguire,  J.  Am.  Chem.  Soc.  28  (1906),  1025. 
Biltz  and  Reinkober,  Ann.  404  (1914),  219.  Mancliot,  Ann.  417  (1918),  93.  Patents, 
Chem.  Abst.  11  (1917),  870,  2027;  12  (1918),  42,  280,  484,  566,  588. 

18  Hofmann  and  Kirmrouther,  Ber.  42  (1909),  4237. 
"Hofmann,  Ber.  31   (1898),  2213. 


OBTAINED  FROM  THE  OLEFINES  119 

The  hydration  of  acetylene  to  form  acetaldehyde  does  not  neces- 
sarily mean  that  the  intermediate  mercury  compounds  have  an  alde- 
hyde structure.  The  hydration  of  the  triple  bond  may  merely  be  cata- 
lyzed by  the  mercuric  ions  in  acid  solution.  Cases  are  known  in 
which  this  hydration  takes  place  under  the  influence  of  dilute  acid 
alone.  Such  a  case  is  that  of  piperonyl  acetylene  which  gives  the 
corresponding  ketone  on  warming  with  dilute  hydrochloric  acid.20 

The  monohalogenated  acetylenes  react  with  alkaline  mercuric  cy- 
anide solution  in  an  atmosphere  of  hydrogen  forming  compounds  of 
the  type  Hg(C  =  CX)2.21 


Mercury  bis-monochloroacetylene,  Hg(C  = 

Monochloroacetylene  is  shaken  with  an  alkaline  solution  of  mer- 
curic cyanide  in  an  atmosphere  of  hydrogen  to  prevent  the  explosion 
which  would  result  from  a  mixture  of  the  monosubstituted  acetylene 
and  air.  A  white  precipitate  is  formed.  This  is  dried  and  extracted 
with  much  warm  ether.  Evaporation  of  the  solution  gives  rectangular 
doubly  refractive  plates.  (CClHg).  M.P.  185°.  If  the  heating  is 
continued  an  explosion  takes  place  which  is  less  violent  than  that  of 
mercury  acetylide.  The  solid  reacts  with  potassium  cyanide  giving 
pure  monochloroacetylene.  The  corresponding  bromine  compound  is 
prepared  in  the  same  way  and  has  similar  properties. 

Methyl  acetylene  (allylene)  reacts  with  mercuric  salts  giving  pre- 
cipitates which  react  with  acids  giving  acetone.  The  intermediate  com- 
pounds are  formulated  as  tri-mercurated  acetones  or  as  double  com- 
pounds of  mercuric  salts  with  mercury  methyl  acetylide.  Allylene 
reacts  with  mercuric  oxide  and  water  giving  mercury  methyl  acety- 
lide, Hg(C^C  —  CH3)2.  (CHHg).22 

Ethyl  acetylene  gives  compounds  much  like  those  of  methyl  acety- 
lene. Treatment  with  acids  gives  methyl  ethyl  ketone.  The  true 
nature  of  the  mercury  compounds  is  not  settled  although  they  may 
well  be  tri-mercurated  compounds  of  the  type 

CH3  —  CH2  —  CO  —  C  (HgX)  3. 

Isopropyl  acetylene  reacts  with  mercuric  bromide  giving  a  product 
which  acts  with  acids  giving  methyl  isopropyl  ketone.23 

»Manchot  and  Haas,  Ann.  399   (1913),  150. 

21  Hofmann  and  Kirmreuther,  Ber.  41    (1908),  31(3;  42   (1909),  423G. 

K  Kutscheroff,  Ber.  17   (1884).  13.     Biltz  and  Muram,  Ber.  37  (1904),  4426. 

"Perkin,  Chem.  Abst.  1   (1913),  2095. 


120  COMPOUNDS  OF  MERCURY 

Methyl  n-butyl  acetylene  reacts  with  mercuric  chloride.24 
Ethyl  propyl  acetylene  gives  a  white  precipitate  with  mercuric  chlo- 
ride which  reacts  with  hydrochloric  acid  giving  an  odor  of  butyrone.25 

Mercury  Compounds  of  Cyclopentadiene  and  Dicyclopentadiene. 

Di- chloromercuri  Cyclopentadiene.26 

Cyclopentadiene  reacts  with  mercuric  chloride  in  alcoholic  solu- 
tion giving  a  white  crystalline  precipitate  insoluble  in  all  solvents. 
(CHCl,Hg  low).  The  white  precipitate  decomposes  in  contact  with 
alcohol  even  with  the  exclusion  of  air  and  light.  It  is  believed  to  be 
a  polymer  because  of  its  insolubility.  This  property  may  simply  be 
due  to  the  presence  of  two  mercury  atoms  on  the  methylene  carbon. 
No  evidence  has  been  secured  as  to  the  structure  of  the  compound. 

Chloromercuri  methoxy  di-cyclopentadiene.*1 

Dicyclopentadiene  does  not  react  with  mercuric  chloride  in  ether 
solution.  If  the  reaction  is  carried  out  in  alcohol  solution  crystalline 
soluble  products  are  obtainable.  These  are  formed  by  the  addition 
of  a  chloromercuri  group  and  an  alkoxyl  group  to  one  of  the  double 
bonds  of  the  dicyclopentadiene.  The  other  double  bond  cannot  be 
made  to  enter  the  reaction. 

Dicyclopentadiene  is  treated  with  mercuric  chloride  in  acetone 
free  methyl  alcohol.  The  solution  is  allowed  to  stand  at  room  tem- 
perature for  two  days  and  is  then  heated  to  boiling  and  diluted  with 
water  until  a  slight  turbidity  forms.  On  standing  fine  crystals 
separate.  The  product  is  obtained  as  slightly  yellowish  needles 
from  60  per  cent  methyl  alcohol.  (CHClHg).  Yield  10  gm. 
from  5  gm.  of  the  hydrocarbon.  M.P.  133°.  It  is  easily 
soluble  in  methyl  and  ethyl  alcohols,  ether,  acetone,  benzene,  gaso- 
line, and  acetic  acid.  Acids  regenerate  dicyclopentadiene  which 
gives  the  characteristic  compound  with  sulfurous  acid.  Boiling 
potassium  cyanide  solution  has  the  same  effect  as  acids.  It  is  soluble 
in  hot  alkalies.  Careful  addition  of  acid  to  the  alkaline  solution  re- 
precipitates  the  chloride.  There  is  no  evidence  as  to  the  positions 
taken  by  the  added  groups.  The  corresponding  ethoxy  compound  is 

*Behal,  Bull.  soc.  cMm.  (2)  49  (1888),  582. 

»B6hal,  Ann.  chim.  phys.  (6)  15   (1888),  415. 

*Thiele,  Ber.  34  (1901),  71.     Hofmann  and  Seller,  Ber.  39  (1906),  3187. 

17  Hofmann  and  Seller,  loc.  cit. 


OBTAINED  FROM  THE  OLEFINES  121 

prepared  by  the  action  of  mercuric  chloride  in  ethyl  alcohol  on  di- 
cyclopentadiene.  Its  properties  are  like  those  of  the  methoxy  com- 
pound. (CHClHg) .  It  forms  colorless  doubly  refractive  prisms.  M.P. 
98°.  The  substance  is  stable  in  a  vacuum  at  80°  showing  that  it 
contains  an  ethoxy  group  rather  than  alcohol  of  crystallization.  The 
molecular  weight  found  by  the  freezing  point  method  in  benzene  is  392, 
calculated  412.5.  The  amyloxy  compound  can  be  prepared  in  isoamyl 
alcohol.  It  is  a  heavy  oil  which  solidifies  at  — 12°  (C  high,  HClHg 
low). 

Mercury  Compounds  from  Unsaturated  Halides. 

Vinyl  bromide  reacts  with  solid  mercuric  acetate  when  heated  at 
100°  for  a  few  hours  forming  an  amorphous  white  precipitate  and 
acetaldehyde.  The  precipitate  is  believed  to  be  a  compound  of  acetal- 
dehyde  with  one  molecule  of  mercurous  bromide.  Heated  to  100°  it 
gives  acetaldehyde.28 

The  mercury  compounds  obtained  from  the  monohalogen  acetylenes 
and  an  alkaline  mercuric  cyanide  solution  have  already  been  de- 
scribed under  acetylene. 

Mercury  bis-trichlorethylene,  Hg(CCl  =  CC12)2.29 

Trichlorethylene  is  shaken  with  an  alkaline  solution  of  mercuric 
cyanide  for  several  days.  The  oily  layer  is  separated  and  the  ex- 
cess of  trichlorethylene  is  distilled  off  under  diminished  pressure.  The 
residue  is  recrystallized  from  ether  or  chloroform.  It  forms  colorless 
shining  plates.  (CClHg).  M.P.  83°.  Chlorine  acts  with  the  compound 
only  in  strong  light  and  then  gives  perchlorethane  and  mercuric  chlo- 
ride. The  corresponding  bromine  compound  is  prepared  from  alkaline 
mercuric  cyanide  and  acetylene  tetrabromide.  Tribromethylene  is 
first  formed  by  the  alkali  and  then  reacts  giving  the  mercury  com- 
pound. Crystalline  leaflets  of  Hg(CN)2.KBr.H20  separate.  An  odor 
of  dibromacetylidine  is  also  noted.  After  ten  hours  the  solid  is  ex- 
tracted with  water,  dried,  and  extracted  with  warm  ether.  After  the 
ether  is  evaporated  the  product  is  dissolved  in  hot  alcohol  and  precipi- 
tated by  water.  The  product  crystallizes  from  ether  in  colorless  doubly 
refractive  prisms.  (CBrHg).  M.P.  141°.  It  is  soluble  in  alcohol  and 

"SaytzeflC  and  Glinsky,  Z.  Chem.  (2)  3  (1867),  675.  Kutscheroff,  B&r.  14  (1881), 
1540. 

•Hofmann  and  Kirmreuther,  Ber.  41  (1908),  314;  42  (1909),  4234. 


122  COMPOUNDS  OF  MERCURY 

ether.  Ammonium  polysulfide  gives  mercuric  sulfide  and  tribromethy- 
lene.  Hot  10  per  cent  hydrochloric  acid  hardly  attacks  it.  Even  hot 
concentrated  potassium  cyanide  solution  acts  only  very  slowly  forming 
tribromethylene. 

Allyl  mercuric  iodide,  CH2  =  CH  —  CH2  —  Hgl.30 

Allyl  iodide  and  an  equal  volume  of  alcohol  are  shaken  with  me- 
tallic mercury.  The  mercury  quickly  reacts  forming  a  yellow  crystal- 
line mass.  A  trace  of  iodine  or  mercurous  iodide  hastens  the  reaction. 
Yield  90  per  cent.  The  product  crystallizes  from  alcohol  in  silvery 
flakes  which  turn  yellow  on  standing.  (CHIHg).  It  is  soluble  in  hot 
alcohol,  carbon  disulfide,  acetone,  almost  insoluble  in  cold  alcohol, 
and  insoluble  in  water.  100  parts  of  carbon  disulfide  at  49°  dissolve 
18.7  parts  of  the  iodide  leaving  a  dark  yellow  residue  of  HgI2.3HgO. 
It  has  a  garlic-like  odor.  It  starts  subliming  at  100°  forming  rhombic 
plates.  M.P.  135°.  Heating  above  the  melting  point  causes  decompo- 
sition giving  a  gas,  carbon,  and  a  yellow  sublimate.  On  standing  it 
changes  in  some  way  to  a  substance  having  a  larger  per  cent  of  mer- 
cury. 

Allyl  mercuric  iodide  reacts  vigorously  with  an  excess  of  cold  po- 
tassium cyanide  forming  mercury,  potassium  iodide,  mercuric  cyanide, 
and  diallyl.  500  gm.  of  allyl  mercuric  iodide  gives  30  gm.  of  diallyl 
and  140  gm.  of  mercury  as  compared  with  the  theoretical  amounts  of 
53  gm.  and  133  gm.  respectively.  A  small  amount  of  an  explosive 
liquid  is  obtained.  This  reaction  is  without  parallel  among  organo- 
mercuric  iodides.  Potassium  cyanide  usually  gives  no  reaction  unless 
heated  with  the  dry  iodide  when  it  gives  a  poor  yield  of  the  mercury 
dialkyl. 

When  the  iodide  is  treated  with  ether  and  an  excess  of  zinc  diethyl 
in  the  cold  a  vigorous  reaction  ensues  forming  a  little  gas,  metallic 
mercury,  zinc  iodide,  diallyl,  and  mercury  diethyl. 

In  marked  contrast  to  the  ease  with  which  allyl  mercuric  iodide  re- 
acts with  potassium  cyanide  and  zinc  diethyl  is  the  fact  that  it  gives  no 
reaction  when  heated  with  phosphorus  tribromide,  acetyl  chloride,  or 
benzoyl  chloride. 

Dry  distillation  of  allyl  mercuric  iodide  gives  metallic  mercury, 
mercuric  iodide,  and  diallyl.  This  is  the  best  method  for  making  that 
substance. 

8°Zinin,  Ann.  90  (18.r.5),  363.  Linnemann,  Ann.  Spl.  3  (1865),  262.  Ann.  140 
(1866),  180.  Oppenheim,  Bcr.  4  (1871),  670. 


OBTAINED  FROM  THE  OLE  FINES  123 

A  paste  of  the  iodide  with  alcohol  reacts  with  the  calculated  amount 
of  iodine  to  form  allyl  iodide  which  can  be  distilled  from  the  mixture. 
This  process  is  used  in  the  separation  of  allyl  iodide  and  isopropyl 
iodide  which  is  based  on  the  fact  that  the  latter  substance  does  not 
react  readily  with  metallic  mercury. 

A  solution  of  the  iodide  in  dilute  nitric  acid  reacts  readily  with 
hydrogen  sulfide  giving  propylene  and  mercuric  sulfide.  Hydriodic 
acid  gives  a  similar  splitting  of  the  C  —  Hg  linkage. 

Allyl  mercuric  iodide  heated  with  allyl  iodide  "probably"  gives 
diallyl  and  mercuric  iodide.31  If  the  reaction  takes  place  in  the  way 
indicated  it  represents  another  peculiar  reaction  of  the  iodide  as  or- 
ganic mercury  compounds  do  not  usually  react  with  organic  halides 
to  form  longer  carbon  chains.  In  this  case  it  would  be  impossible 
to  follow  the  course  of  the  reaction  as  allyl  mercuric  iodide  itself  gives 
diallyl  on  heating.  The  mercury  formed  could  react  with  the  allyl 
iodide  present  forming  more  allyl  mercuric  iodide  which  would  pro- 
duce more  diallyl. 

The  iodide  reacts  with  alcoholic  silver  nitrate  giving  a  solution  of 
allyl  mercuric  nitrate.  In  a  similar  way  moist  silver  oxide  gives  an 
alcoholic  solution  of  the  hydroxide  which  is  obtained  as  a  syrup  on 
evaporation.  This  is  volatile  on  heating  and  has  an  odor  of  garlic. 
It  reacts  with  acids  forming  salts. 

Propargyl  mercuric  iodide,  CH  =  C  —  CH2  —  Hgl.32 

Propargyl  iodide  unites  readily  with  metallic  mercury.  The  prod- 
uct has  not  been  studied  in  detail. 

Mercury  Derivatives  of  Aliphatic  Nitro  Compounds.33 

The  mercury  derivatives  of  the  nitro  compounds  were  originally 
believed  to  be  C  —  Hg  compounds  in  much  the  same  way  that  the 
sodium  derivatives  were  believed  to  have  the  sodium  attached  to  car- 
bon. In  all  probability  they  are  O  —  Hg  compounds.  Mercury  bis- 
nitroform  is  possibly  an  exception.  In  some  solvents  it  gives  a  color- 
less solution  which  is  a  non-conductor.  Such  solvents  are  ether,  ben- 

31  Linnemann,  loc.  cit. 

82  Henry,  Ber.  17   (1884),  li32. 

33  V.  Meyer,  Ber.  5  (1872),  516.  Meyer  and  Rilliet,  ibid.  1030.  Meyer,  Ann.  171 
(1874),  31.  Nef,  Ann.  280  (1894),  270.  L.  W.  Jones,  Am.  Chem.  J.  20  (1898),  33. 
Ley  and  Kissel,  Ber.  32  (1899),  1357.  Ley,  Ber.  38  (1905),  974.  Scholl  and  Nyberg, 
Ber.  39  (1906),  1958.  Prager,  Monatsh.  33  (1912),  1289. 


124  COMPOUNDS  OF  MERCURY 

zene  and  its  homologs,  ethyl  acetate,  ethyl  oxalate,  chloroform,  car- 
bon tetrachloride,  and  lactic  acid.  It  gives  colored  ionized  solutions 
in  water  and  pyridine.  It  has  been  suggested  that  the  colorless  form 
is  a  C  —  Hg  compound  and  the  colored  an  0  —  Hg  compound.3* 

Hg[C(NO,),],  [(02N)2C  =  N-0-]2Hg 

Colorless  Colored 

Non-ionized.  Ionized. 

84  Ley  and  Kissel,  loc.  cit.     Ley,  loc.  cit. 


Chapter  VI. 

Mercury  Compounds  from  Saturated  and  Unsaturated 

Alcohols. 

Ethyl  alcohol  reacts  with  mercuric  salts  and  with  mercuric  salts  in 
the  presence  of  alkalies  giving  a  variety  of  ill  defined  compounds.1  The 
only  compounds  of  settled  constitution  are  the  mercarbides. 

Alcohols  cause  a  splitting  of  mercuric  salts  of  oxygen  acids  analo- 
gous to  hydrolysis.  This  alcoholysis  appears  to  be  more  rapid  with  iso- 
propyl  and  isobutyl  alcohols  than  with  the  normal  compounds.2 

Tertiary  alcohols  heated  with  an  acid  solution  of  mercuric  sulfate 
give  a  yellow  precipitate  containing  mercury.  On  further  heating  mer- 
curous  sulfate  is  formed.  This  reaction  has  been  recommended  as  a 
test  for  tertiary  alcohols.8 

Mercarbides. 

Mercarbides  are  compounds  having  all  of  the  hydrogen  of  a  methyl 
group  replaced  by  mercury.4 

Ethane  hexamer carbide,  C2Hg602(OH)2. 

Yellow  mercuric  oxide,  potassium  hydroxide,  and  ordinary  alcohol 
are  heated  together  under  a  reflux  condenser  for  36  hours.  The  grayish 
yellow  residue  is  washed  with  water  and  dilute  alkali  and  then  with 
20  per  cent  warm  nitric  acid  to  dissolve  any  mercury  or  tri-mercurated 
acetic  acid  present.  The  residue  is  the  dinitrate  of  the  mercarbide, 
C2Hg602(N03)2.  It  is  pure  white.  The  mercarbide  itself  is  obtained 

iSobrero  and  Selmi,  Ann.  80  (1851),  108.  Jahresb.  (1815),  506.  Gerhardt,  Ann. 
80  (1851),  111.  Reynoso,  Ann.  chim.  plvys.  (3)  48  (1856),  403.  Cowper,  J.  Chem. 
Soo.  39  (1881),  242.  Dimroth,  Ber.  31  (1898),  2156.  Marsh  and  Struthers,  J.  Chem. 
Soc.  95  (1909),  1778. 

2  Schoeller,  Schrauth,  and  Struensee,  Ber.  44   (1911),  1052  ff. 

"Denig&s,  Ann  chim.  phys.  (7)  18  (1899),  393.  Bull.  soc.  chim.  (3)  19  (1898), 
751. 

*Hofmann,  B0r.  31  (1898),  1904,  2213;  32  (1899>,  870;  33  (1900),  1328.  Hof- 
mann  and  Sand,  Ber.  33  (1900),  1358.  Hofmann  and  Feigel,  Ber.  38  (1905),  3654. 
Hofmann  and  Wagner,  Ber.  41  (1908),  1628. 

125 


126  COMPOUNDS  OF  MERCURY 

by  treating  the  nitrate  with  pure  sodium  hydroxide.  The  presence 
of  any  chloride  will  change  part  of  the  mercury  base  into  the  chloride. 
The  base  is  slightly  yellow.  (CHHg).  Yield,  57  gm.  of  the  mercarbide 
from  100  gm.  of  mercuric  oxide.  About  40  per  cent  of  the  mercuric 
oxide  used  is  reduced  to  metallic  mercury.  About  2  per  cent  of  tri- 
mercuri-acetic  acid  is  obtained.  Considerable  amounts  of  aldehyde 
resin  and  oxalic  acid  are  also  formed. 

The  probable  course  of  the  reaction  is  as  follows:  the  alcohol  is 
first  oxidized  by  one  molecule  of  mercuric  oxide  to  acetaldehyde  which 
is  then  mercurated  by  three  molecules  of  mercuric  oxide  giving  the 

Hg  HgOH 

/      \    / 

anhydride  of  tri-hydroxymercuri   acetaldehyde,   O  C 

\       /    \ 
Hg  CHO 

This  is  oxidized  by  another  molecule  of  the  oxide  to  the  sodium  salt 
of  the  corresponding  tri-mercuri  acetic  acid.  Two  molecules  of  this 
substance  lose  sodium  oxalate  leaving  the  mercarbide, 

0  — Hg      Hg  — 0 


[g-C-C-Hg     . 

HO  — Hg      Hg  — OH 

This  mechanism  would  call  for  a  yield  of  60  gm.  of  mercarbide  from 
100  gm.  of  oxide  whereas  57  gm.  are  obtained. 

The  mercarbide  can  also  be  obtained  from  acetaldehyde,  propyl 
alcohol,  allyl  alcohol,  amyl  alcohol,  cellulose,  and  starch.  Methyl  alco- 
hol and  formaldehyde  give  none  of  it. 

The  mercarbide  base  is  a  yellowish  white  very  insoluble  powder. 
It  reacts  with  acids  forming  salts  which  are  very  stable  to  an  excess  of 
acid,  hydrogen  sulfide,  potassium  cyanide,  and  even  aqua  regia.  It 
is  also  stable  to  powerful  oxidizers  such  as  potassium  permanganate, 
chromic  acid,  hypochlorites  and  hypobromites.  It  reacts  very  slowly 
with  reducing  agents  such  as  sulfurous  acid,  hydroxylamine,  and  hy- 
drazine.  When  heated  it  explodes  at  about  230°  with  extreme  brisance. 
It  is,  however,  stable  to  concussion. 

Treatment  of  the  mercarbide  with  acids  gives  two  sets  of  salts, 
one  in  which  the  two  hydroxyl  groups  have  been  replaced  by  acid  radi- 
cals and  the  other  in  which  all  of  the  oxygen  groups  have  been  replaced 


FROM  SATURATED  AND  UNSATURATED  ALCOHOLS     127 

giving  salts  of  the  type  C2Hg6X6.  Hydrogen  sulfide  reacts  with  the 
mercarbide  giving  a  complex  sulfide  but  no  mercuric  sulfide.  The 
extraordinary  stability  of  the  C  —  Hg  linkages  in  this  substance  can 
be  shown  by  the  fact  that  treatment  of  this  sulfide  with  chlorine  water, 
nitric  acid,  and  sodium  hydroxide  gives  the  original  hexamercarbide. 
(CHHg). 

A  methyl  alcohol  solution  of  ammonium  polysulfide  acts  slowly 
on  the  mercarbide.  If  the  mixture  is  allowed  to  stand  for  several  weeks 
with  frequent  renewals  of  the  polysulfide  solution  the  mercarbide  is 
finally  changed  to  a  deep  yellow  powder.  If  this  is  treated  with  hy- 
drogen sulfide  it  turns  black.  Treatment  with  potassium  sulfide  re- 
stores the  yellow  color.  The  yellow  substance  is  very  insoluble.  It 
has  the  formula  C2Hg602S2H2.  (CHSHg) .  It  has  two  atoms  of  sulfur 
in  place  of  two  atoms  of  oxygen  in  the  original  mercarbide. 

The  mercarbide  reacts  with  a  10  per  cent  solution  of  sulfur  mono- 
chloride  in  benzene  forming  mercuric  chloride  and  an  intensely  yellow 
crystalline  compound,  (ClHg)2C  — C(HgCl)2.  (CClSHg).  This  is 


_ 


insoluble  in  all  solvents.  It  is  stable  to  boiling  concentrated  hydro- 
chloric acid.  When  heated  with  sodium  hydroxide  it  gives  a  dark 
yellow  product  which  does  not  explode  on  heating. 

Long  boiling  with  hydrazine  hydrate  gives  a  mixture  of  nitrogen 
and  a  combustible  gas  which  is  probably  ethane. 

When  the  mercarbide  is  heated  it  turns  dark  red  before  it  explodes. 
This  change  of  color  may  be  due  to  the  loss  of  another  molecule  of 
water  leaving  a  compound  C2Hg603  which  is  the  real  explosive  sub- 
stance. The  products  of  the  explosion  contain  mercury,  carbon  di- 
oxide, and  other  substances. 

The  mercarbide  reacts  with  an  excess  of  sodium  bisulfite  solution 
giving  a  light  yellow  substance  which  turns  gray  in  light.  If  the  yel- 
low substance  is  treated  with  nitric  acid  and  then  boiled  with  pure 
sodium  hydroxide  the  original  mercarbide  is  recovered. 

The  mercarbide  forms  a  picrate  which  is  less  explosive  than  potas- 
sium picrate. 

Long  boiling  of  the  mercarbide  with  potassium  cyanide  solution 
gives  an  intensely  yellow  solid  of  lower  specific  gravity  than  .the 
original  substance.  Its  formula  is  C2Hg4(CN)2.  (CNHg).  Its  struc- 


128  COMPOUNDS  OF  MERCURY 

ture  is  probably  Hg  =  C  —  C  =  Hg.      It  explodes  slightly  on  heating. 

CN  — Hg    Hg  — CN 

It  is  soluble  in  cold  15  per  cent  nitric  acid.  Treatment  of  this  solu- 
tion with  hydrogen  sulfide  gives  a  white  precipitate  of  a  compound, 
C2Hg4S2H2,  which  is  probably  the  sulf hydrate  corresponding  to  the 
cyanide  used.  (CHSHg) .  The  cyanide  reacts  with  hydrochloric  acid 
forming  hydrocyanic  acid  and  a  compound,  C2Hg4Cl4H2,  which  prob- 
ably has  the  structure  of  a  tetra-mercurated  ethane,  (ClHg)  2CH  —  CH 
(HgCl)2.  If  this  substance  is  heated  with  concentrated  hydrochloric 
acid  it  gives  a  crystalline  volatile  compound  having  the  formula 
ClHg  —  CH2  —  CH2  —  HgCl.  (CHClHg).  This  substance  separates 
in  the  condenser  and  receiver  in  colorless  rectangular  leaflets.  It  has 
an  intense  odor  somewhat  resembling  that  of  hydrocyanic  acid.  It  is 
volatile  even  at  room  temperature.  It  is  easily  soluble  in  water,  alco- 
hol, and  ether.  M.P.  173°.  It  is  rather  poisonous.  A  solution  in 
hydrochloric  acid  acts  with  potassium  iodide  giving  white  needle 
crystals  which  are  not  attacked  by  dilute  acids  but  dissolve  in  bases. 
This  iodide  can  be  recrystallized  from  alcohol  and  ether  in  quadratic 
plates.  When  the  tetramercarbide  dicyanide,  Hg  =  C  —  C  =  Hg  , 

CN  — Hg   Hg  — CN 

is  treated  with  an  aqueous  solution  of  potassium  polysulfide  it  is 
changed  to  a  yellow  precipitate,  C4Hg4SH6.  (CHSHg) .  This  may  be 
an  organic  sulfide,  (Hg  =  CH  —  CH2  —  Hg  — )  2S.  If  ammonium 
polysulfide  in  methyl  alcohol  is  used  instead  of  the  aqueous  potassium 
polysulfide  the  product  is  a  yellow  substance  having  the  formula, 

C2Hg2SH4.     (CHSHg).    This  is  probably  CH2  — Hg      . 

S 
JH2-Hg 

Ethane  hexamercarbide  dichloride,  C2Hg602Cl2. 

This  substance  is  prepared  from  the  mercarbide  and  a  hot  chloride 
solution  or  cold  10  per  cent  hydrochloric  acid.  (Cl).  It  reacts  with 
ammonia  giving  a  yellow  white  compound,  C2Hg602(NH3)2Cl2. 
(NClHg). 

The  corresponding  nitrate,  sulf  ate,  and  p&rchlorate  have  been  pre- 
pared and  analyzed. 


FROM  SATURATED  AND  UNSATURATED  ALCOHOLS     129 

Ethane  hexamercarbide  hexachloride,  (ClHg)3C  —  C(HgCl)3. 

Ethane  hexamercarbide  is  heated  with  10  per  cent  hydrochloric 
acid.  The  product  is  a  white  insoluble  substance.  (CClHg).  It  de- 
composes quietly  on  heating.  Boiling  with  sodium  hydroxide  gives 
the  original  base.  When  treated  with  a  water  solution  of  potassium 
polysulfide  in  the  dark  it  gives  yellow  crystals  of  a  compound, 
ClHg  — CH-  -CH  — HgCl.  (CHClSHg).  Boiling  hydrochloric 

Hg  — S  — Hg 

acid  gives  an  odor  like  that  of  the  di-chloromercuri  ethane  mentioned 
above.  A  white  crystalline  product  is  obtained  at  the  same  time.  This 
reacts  with  sodium  hydroxide  to  form  a  yellow  non-explosive  com- 
pound. Treatment  of  the  hexachloride  with  sulfur  monochloride  dis- 
solved in  benzene  or  undiluted  gives  no  action. 

The  corresponding  hexa-iodide,  C2Hg6I6,  is  obtained  on  heating 
ethane  hexamercarbide  with  ethyl  iodide  and  ether  for  60  hours  at  90°. 
(CIHg). 

The  remarkable  reactions  noted  in  the  study  of  ethane  hexamercar- 
bide are  summarized  in  the  chart  on  page  130. 

Mercarbides  from  Acetylene.5 

Acetylene  passed  into  a  cold  mercuric  nitrate  solution  gives  a 
precipitate  which  may  have  the  structure,  Hg  =  C  —  CHO,  (Hg) . 

\ 
HgN03 

Acetylene  passed  into  a  solution  of  mercuric  chloride  and  sodium  chlo- 
ride gives  a  precipitate  which  may  be  (ClHg)2C  —  CC12.  (C,C1  low,Hg 

\   / 
Hg 

low) .  Long  washing  with  water  lowers  the  chlorine  content  still  more. 
Boiling  dilute  hydrochloric  acid  gives  considerable  acetaldehyde. 

Mercarbides  from  Acetic  Acid.6 

Sodium  acetate  refluxed  with  mercuric  chloride  in  absolute  alcohol 
for  20  hours  gives  a  white  crystalline  powder  which  is  purified  by  ex- 
traction with  15  per  cent  warm  nitric  acid  and  then  with  30  per  cent 
cold  nitric  acid.  (CClHg).  The  same  product  can  be  obtained  from 

'Hofmann,  Ber.  31    (1898),  2213,  2783;  32   (1899),  870. 
•Hofmann,  Ber.  32  (1899),  870, 


130 


COMPOUNDS  OF  MERCURY 


FROM  SATURATED  AND  UNSATURATED  ALCOHOLS     131 

sodium  propionate  or  sodium  butyrate.  The  white  substance  is  black- 
ened by  bases  and  by  potassium  cyanide.  It  might  indeed  be  mis- 
taken for  mercurous  chloride  but  for  the  fact  that  it  is  partly  soluble 
in  hot  sodium  hydroxide.  The  treatment  with  bases  or  cyanides  gives 
an  odor  of  acetaldehyde.  The  solution  obtained  by  means  of  hot 
sodium  hydroxide  contains  tri-mercuri-acetic  acid  and  some  of  the 
corresponding  di-mercuri  compound.  The  original  substance  prob- 
ably has  the  structure  (ClHg)2C  — C  —  HgCl. 

\   /  \ 
Hg       Cl 

Other  Mercarbides. 

Potato  starch  gives  a  mercarbide,  C3Hg202H6(N03). T 

Acetone  gives  C3Hg303H5. 8 

Cane  sugar  gives  C3Hg400HG(N03). 9 

Mercury  Compounds  of  Unsaturated  Alcohols. 

Vinyl  Alcohol.10 

Crude  diethyl  ether  shaken  with  mercury  oxychloride,  HgO.HgCl2, 
gives  a  precipitate  to  which  is  assigned  the  formula 

"CH2  =  CHOHgOHgCy. 

(CHClHg) .  It  is  blackened  by  bases.  It  dissolves  in  acetic  acid  giv- 
ing a  crystalline  acetate. 

Allyl  Alcohol11 

Considerable  work  has  been  done  on  the  action  of  mercuric  salts 
on  allyl  alcohol  and  the  products  obtained  have  been  formulated  in  a 
variety  of  ways.  The  problem  like  all  those  involving  the  action 
of  mercuric  salts  with  unsaturated  compounds  cannot  be  regarded  as 
settled.  It  seems  probable  that  only  two  classes  of  compounds  are 
obtained,  the  propylene  glycol  mercuric  salts  of  the  type 
CH2OH  —  CHOH  —  CH2HgX,  and  the  dipropylene  oxide  di-mercuric 
salts  of  the  type  XHgCH2  —  CH  —  CH2  —  0  .  The  lat- 

0  —  CH2  —  CH  — CH2HgX 

7  Hofmann,  Ber.  33   (1900),  1333. 

8Hofmann,  Ber.  31   (1898),  1908. 

•Hofmann,  Ber.  33   (1900),  1333. 

10Poleck  and  Thiimmel,  Arch.  Pharm.  Nov.  1889.     Ber.  22   (1889),  1866. 

11  Hofmann  and  Sand,  Ber.  33  (1900),  1358.  Biilmann,  ibid.  1641.  Hofmann  and 
Sand,  ibid.  2692.  Sand,  Ber.  34  (1901),  1385,  2906.  Biilmann,  Ber.  35  (1902),  2586. 
Sand  and  Singer,  ibid.  3170, 


132  COMPOUNDS  OF  MERCURY 

ter  compounds  have  been  incorrectly  formulated  as  allene  mercuric 
compounds,  CH2  =  C  =  CH  —  HgX;  as  allyl  alcohol  mercuric  com- 
pounds, CH2OH  —  CH  =  CH  —  HgX;  and  as  propylene  oxide  mercuric 
compounds,  CH2  —  CH  —  CH2  —  HgX  or  CH2  —  CH  (HgX)  —  CH2. 


The  propylene  glycol  mercuric  salts  are  made  by  treating  basic  mer- 
curic nitrate  with  allyl  alcohol  and  precipitating  the  alkaline  solution 
with  potassium  iodide,  etc.  The  dipropylene  oxide  di-mercuric  salts 
are  obtained  by  allowing  allyl  alcohol  to  react  on  an  acid  solution 
of  mercuric  nitrate  forming  crystals  of  the  organic  mercuric  nitrate 
which  can  be  dissolved  in  alkali  and  precipitated  by  potassium  halides. 
The  formation  of  the  two  types  of  products  is  explained  by  assuming 
that  the  first  stage  in  the  reaction  is  the  addition  of  —  X  and  —  HgX 
to  the  double  bond  forming  an  unstable  product,  CH2OH  —  CHX  — 
CH2HgX.  In  the  presence  of  alkali  the  acid  group  on  the  middle 
carbon  is  hydrolyzed  off  giving  a  propylene  glycol  mercuric  salt.  In 
acid  solution  this  does  not  take  place  but  two  molecules  react  with 
the  elimination  of  two  molecules  of  HX  forming  a  dipropylene  oxide 
compound  containing  a  six  membered  ring  having  the  same  structure 
as  di-epi-iodhydrine  which  probably  has  the  structure 

I  —  CH2  —  CH  —  CH2  —  0 


0  — CH,  —  CH- 


PTT 

LO  V-/-I.J.  V^J-Ao   "  -1* 

The  difference  in  the  two  types  of  compounds  obtained  from  allyl 
alcohol  are  well  shown  by  a  comparison  of  the  properties  of  the  two 
bromides.13 

Propylene  glycol  compound.  Di-propylene  oxide  compound. 
C3H702  —  HgBr.  (C3H50  —  HgBr)  2. 

M.P.  84-6°.  M.P.  251°. 

Easily  soluble  in  alcohol  and  Insoluble  in  organic  solvents, 
acetone. 

Easily  decomposed  by  HC1.  Not  changed  by  HC1. 

Alkaline  solution  gives  no  ac-  KI  forms  a  white  precipitate, 
tion  with  KI. 

Ditto  +  KCN  gives  no  action.  KCN  forms  a  white  precipitate. 

Ditto  +  H2S  gives  no  action.  H2S  forms  a  white  precipitate. 

"Stoehr,  J.  prakt.  Ohem.  (2)  55  (1897),  88. 
"fjpfmann  an4  Sand,  Ber.  33  (1900),  2700, 


FROM  SATURATED  AND  UNSATURATED  ALCOHOLS     133 

Proylene  glycol  mercuric  iodide,  CH2OH  —  CHOH  —  CH2  —  Hgl. 14 
Yellow  mercuric  oxide  is  dissolved  in  20  per  cent  nitric  acid  and 
the  solution  is  treated  with  pure  dilute  potassium  hydroxide  until  a 
slight  permanent  precipitate  of  the  basic  nitrate  is  formed.  Allyl  alco- 
hol is  added  and  the  mixture  is  shaken  until  the  precipitate  dissolves. 
More  base  is  added  to  form  a  precipitate  and  the  precipitate  is  dis- 
solved in  more  allyl  alcohol.  The  alternate  addition  of  base  and  allyl 
alcohol  is  continued  until  the  addition  of  base  gives  a  black  precipi- 
tate. The  alkaline  solution  is  filtered,  treated  with  potassium  iodide 
solution,  allowed  to  stand  24  hours,  and  saturated  with  carbon  dioxide. 
A  yellow  viscous  oil  separates  which,  when  dried,  forms  a  crystalline 
mass  containing  some  drops  of  mercury.  'This  is  crystallized  from 
benzene  or  dry  ether  in  which  it  is  difficultly  soluble.  A  better  method 
of  purification  is  by  dissolving  it  in  alcohol  or  acetone,  decolorizing 
the  solution  with  bone  black,  adding  one-fifth  volume  of  benzene,  and 
evaporating  in  vacuo.  The  substance  forms  white  plates  melting 
at  80°.  (CHHg).  Hydrochloric  acid  or  even  acetic  acid  after  a  few 
minutes  standing  gives  mercuric  salts  and  allyl  alcohol. 

A  solution  of  the  iodide  in  10  per  cent  potassium  hydroxide  re- 
acts on  shaking  with  benzoyl  chloride  giving  a  dibenzoyl  derivative, 
C6H5  —  CO  —  OCH2.  It  is  best  purified  by  dissolving  in  alcohol  and 

CJL  —  co  —  OCH 


GIL 


[2-HgI 

pouring  into  potassium  iodide  solution.    M.P.  100°.   (CH).  It  is  stable 
to  fuming  hydrochloric  acid. 

The 'corresponding  bromide  is  prepared  the  same  as  the  iodide.  It 
is  purified  by  dissolving  in  acetone,  adding  benzene,  and  concentrating 
in -a  vacuum.  White  crystals.  (CHBrHg).  On  rapid  heating  it  melts 
84-6°.  At  110°  it  decomposes  with  evolution  of  gas.  It  is  more  solu- 
ble in  water  than  the  iodide.  It  is  easily  soluble  in  alcohol  and  acetone. 
It  is  rapidly  decomposed  by  hydrochloric  acid. 

Di-mercuri  Compounds  of  Di-propylene  oxide. 
XHg  — CH2  — CH  — CH2  —0 

0  — CH2  — CH  — CH2  — HgX  . 

"Hofmann  and  Sand,  Ber.  33  (1900),  2698. 


134  COMPOUNDS  OF  MERCURY 

The  nitrate  has  probably  never  been  obtained  in  a  pure  state.  If  a 
fairly  strongly  acid  solution  of  mercuric  nitrate  is  treated  with  allyl 
alcohol  an  exothermic  reaction  takes  place.  The  solution  must  be 
cooled  to  0°  to  avoid  the  formation  of  extremely  insoluble  products. 
After  several  days  a  large  amount  of  a  crystalline  substance  sepa- 
rates. It  is  soluble  in  alkalies  and  ammonium  hydroxide.  Ammonium 
sulfide  and  hydrogen  sulfide  gives  white  precipitates.  It  reacts  with 
halides  and  cyanides  to  form  the  corresponding  organomercuric  salts. 
The  solution  in  ammonium  hydroxide  deposits  fine  white  crystals  of  a 
compound  containing  ammonia.  The  nitrate  may  also  be  obtained  by 
treating  allyl  alcohol  with  mercurcws  nitrate.  In  this  case  metallic 
mercury  is  formed. 

The  sulfate  is  obtained  from  allyl  alcohol  and  an  acid  solution  of 
mercuric  sulfate.15  The  reaction  mixture  must  be  kept  cooled  to  20°. 
It  is  soluble  in  water  and  in  base  solutions.  It  can  be  purified  by 
crystallization  from  water  containing  a  little  allyl  alcohol.  It  then 
contains  4H20.  (CHHg,S04,H2O).  It  forms  a  compound  with  two 
molecules  of  ammonia.  (S04,NH3).  When  treated  with  bromine  it 
gives  the  corresponding  bromide  if  an  excess  of  the  halogen  is  avoided. 

The  chloride  is  prepared  by  treating  an  alkaline  solution  of  the  ni- 
trate with  dilute  hydrochloric  acid  or  potassium  chloride  and  car- 
bon dioxide.  (CHHg) .  Another  preparation  is  from  a  complex  double 
compound  of  mercuric  chloride  formed  from  mercuric  chloride  solution 
and  allyl  alcohol.16  This  compound  is  treated  with  10  per  cent  alkali 
which  converts  one-third  of  the  mercury  in  the  compound  into  mer- 
curic oxide.  The  filtrate  when  saturated  with  carbon  dioxide  gives  a 
precipitate  of  the  chloride.  (CHC1  low,  Hg).  The  chloride  reacts  with 
zinc  and  dilute  hydrochloric  acid  giving  an  odor  of  allyl  alcohol.  Boil- 
ing with  20  per  cent  hydrochloric  acid  gives  mercuric  chloride  and  a 
variety  of  compounds  including  allyl  chloride,  allyl  ether,  propylene 
glycol,  methyl  ethyl  acrolein,  and  propionaldehyde.  Potassium  per- 
manganate oxidizes  the  chloride  giving  oxalic  acid  among  other 
products. 

The  bromide  is  prepared  in  the  same  way  as  the  chloride.  It  is 
almost  insoluble  in  organic  solvents.  (CHBr).  M.P.  251°.  Its  molecu- 
lar weight  by  the  boiling  point  method  in  ethylene  dibromide  is  found 
to  be  605  as  compared  with  the  calculated  value  of  674. 

"Biilmann,  Ber.  33    (1900),  1642. 
"Hofinann  and  Sand,  Ber.  33   (1900),  1359. 


FROM  SATURATED  AND  UNSATURATED  ALCOHOLS     135 

An  alkaline  solution  of  the  bromide  reacts  with  sodium  stannite 
giving  a  brick  red  precipitate  of  an  organic  mercurows   compound, 

O CH2 


CH  — CH2  — Hg  — Hg  — CH2  — CH.      (CHHg  low).     Standing   in 


sunlight  changes  this  red  substance  to  a  gray  powder  from  which  hot 
benzene  extracts  a  substance  which  appears  in  colorless  crystals  when 
the  benzene  solution  is  treated  with  acetone  and  cooled.  This  sub- 
stance is  the  corresponding  murcuric  compound, 

O CH2 


CH2  — Hg  — CH2  — CH. 


Poor  yield.  (CHHg).  M.P.  about  190°.  It  is  insoluble  in  water,  po- 
tassium hydroxide,  dilute  acids,  easily  soluble  in  benzene  and  toluene, 
and  insoluble  in  acetone.  It  is  not  changed  by  boiling  with  potassium 
hydroxide,  iodide,  or  cyanide.  A  benzene  solution  gives  a  precipitate 
with  mercuric  chloride  dissolved  in  ether.  This  may  well  be  the  di- 
chloromercuri  di-propylene  oxide. 

The  iodide,  IHg  —  CH2  —  CH  —  CH2  —  0  ,  is 

0  —  CH2  —  CH  —  CH2  —  Hgl 

prepared  from  an  alkaline  solution  of  the  nitrate  and  potassium  iodide 
solution.  In  this  case  no  carbon  dioxide  is  needed  to  cause  precipita- 
tion as  the  iodide  differs  from  the  chloride  and  bromide  in  not  being 
soluble  in  cold  alkalies.  The  iodide  can  be  recrystallized  from  boil- 
ing alkali.  (CHIHg).  M.P.  271°.  It  is  practically  insoluble  in  the 
common  organic  solvents  but  can  be  recrystallized  from  boiling  benzyl 
chloride.  This  is  a  good  example  of  the  failure  of  organic  mercury  com- 
pounds to  react  with  organic  halides.  The  iodide  is  not  changed  by  20 
per  cent  hydrochloric  acid.  The  hot  alkaline  solution  gives  a  precipi- 
tate with  potassium  cyanide.  The  iodide  reacts  but  slowly  with  iodine 
in  potassium  iodide  solution.  It  reacts  with  iodine  in  benzene  in  a 


136  COMPOUNDS  OF  MERCURY 

tube  at  140°  giving  di-epi-iodohydrine  which  probably  has  the  struc- 
ture, ICH2  — CH  — CH2  — 0  ,17 

0  — CH2  — CH  — CH2I 

The  cyanide  is  prepared  from  the  alkaline  solution  of  the  nitrate 
by  adding  potassium  cyanide.  It  forms  a  thick  white  precipitate 
which  is  insoluble  in  alkali  even  on  heating.  (CHNHg) . 

The  hydroxide  is  prepared  from  the  chloride  and  moist  silver  oxide. 
The  water  solution  is  alkaline  and  precipitates  the  hydroxides  of  heavy 
metals  from  their  solutions.  The  same  hydroxide  is  probably  obtained 
by  allowing  allyl  alcohol  and  water  to  react  on  freshly  prepared  yellow 
mercuric  oxide.  The  alkaline  solution  so  prepared  reacts  with  hydro- 
bromic  acid  forming  di-bromomercuri  di-propylene  oxide.  (Br) . 

The  acetate  is  obtained  from  allyl  alcohol  and  an  acid  solution  of 
mercuric  acetate.  It  forms  a  white  crystalline  precipitate.  When 
dried  over  calcium  chloride  it  retains  half  a  molecule  of  water.  (CHHg) . 
When  recrystallized  from  hot  water  it  is  obtained  anhydrous.  (CHHg). 
It  gives  precipitates  with  potassium  bromide  and  with  dilute  hydro- 
chloric acid.  It  dissolves  in  alkalies  and  in  ammonium  hydroxide. 
Ammonium  sulfide  gives  a  white  precipitate.  Boiling  in  water  does  not 
decompose  the  acetate. 

A  basic  carbonate  is  obtained  by  passing  carbon  dioxide  into  an 
alkaline  solution  of  the  nitrate.  The  precipitate  contains  one  molecule 
of  the  carbonate  for  three  of  the  hydroxide.  (CHHg,C02). 

"Stoehr,  J.  prakt.  Ohem.  (2)  55  (1897),  88. 


Chapter  VII. 
Mercury  Derivatives  of  Fatty  Acids. 

Mercury  Compounds  from  Carbon  Monoxide.1 

Mercuric  salts  in  alcohol  add  to  carbon  monoxide  in  much  the  same 
way  that  they  add  to  ethylene  compounds.  As  in  the  case  of  all  such 
reactions  the  products  may  be  formulated  as  true  structure  compounds 

HgX 

/ 

or    as    molecular    addition    compounds,    C  =  0     or    CO.Hg(OR)X. 

\ 
OR 

Neither  formula  explains  all  of  the  reactions.  Acids  and  alkyl  halides 
liberate  carbon  monoxide,  a  fact  which  throws  doubt  on  the  first 
formula.  Various  reactions  give  formic  acid  derivatives,  a  fact  which 
is  hard  to  explain  by  the  second  formula. 

Acetoxymercuriformic  methyl  ester,  AcOHg  —  C02CH3. 

A  methyl  alcohol  solution  of  mercuric  acetate  is  treated  with  car- 
bon monoxide  under  two  atmospheres  pressure  in  a  specially  con- 
structed shaking  apparatus.  The  gas  is  absorbed  slowly  for  about  24 
hours.  Almost  exactly  one  mole  is  absorbed.  Small  amounts  of  mer- 
curous  acetate  and  carbon  dioxide  are  formed.  The  reaction  mixture 
is  filtered  and  the  filtrate  is  evaporated  under  diminished  pressure  at 
about  35°.  An  oil  is  left  which  solidifies  on  standing.  The  solid  is 
dissolved  in  chloroform  by  gentle  warming  and  then  treated  with  five 
volumes  of  40-60°  ligroin.  Crystals  soon  separate.  (CHHg).  Yield  88 
per  cent.  Correcting  for  the  mercurous  acetate  formed  the  yield  is 
95  per  cent.  On  rapid  heating  it  melts  109°  (corr.  110°)  with  decom- 
position. It  is  easily  soluble  in  methyl  and  ethyl  alcohols,  chloroform, 
fairly  soluble  in  warm  water,  ethylacetate,  acetone,  and  benzene,  diffi- 

'Schoeller  and  Schrauth,  Ber.  46   (1913),  2869.     Manchot,  Ber.  53  (1920),  984. 

137 


138  COMPOUNDS  OF  MERCURY 

cultly  soluble  in  ether  and  low  and  high  boiling  ligroin.  Heating  gives 
carbon  monoxide,  mercurous  acetate  and  other  products  which  have  not 
been  identified.  Its  molecular  weight  by  the  boiling  point  method  in 
chloroform  is  310  as  compared  with  the  calculated  value  of  318.  A 
freshly  prepared  sample  of  the  acetate  is  completely  soluble  in  am- 
monium hydroxide  without  the  formation  of  any  black  product.  Am- 
monium sulfide  does  not  give  mercuric  sulfide  until  the  mixture  has 
stood  for  a  few  minutes.  The  other  product  is  carbon  monoxide. 

.1  normal  halogen  acids  precipitate  the  corresponding  halogen  mer- 
curi  compound.  5.  normal  halogen  acid  gives  carbon  monoxide  imme- 
diately. Concentrated  sulfuric  acid  evolves  almost  exactly  one  mole 
of  carbon  monoxide.  Cold  dilute  nitric  acid  and  acetic  acid  give  only 
a  slow  decomposition.  Hot  dilute  nitric  acid  liberates  carbon  dioxide 
instead  of  the  monoxide.  Normal  sodium  hydroxide  dissolves  the  ace- 
tate giving  a  clear  solution  from  which  mercury  soon  separates  leav- 
ing a  solution  of  sodium  bicarbonate.  When  the  mercurated  ester  is 
heated  with  methyl  iodide  at  100°  it  gives  mercuric  iodide,  mercuric 
acetate,  and  almost  exactly  one  mole  of  carbon  monoxide. 

Acetoxymercuriformic  ethyl  ester. 

It  is  prepared  in  the  same  way  as  the  methyl  ester.  In  ethyl  alco- 
hol solution  the  absorption  of  the  carbon  monoxide  takes  three  times 
as  long  as  in  methyl  alcohol.  Needle  crystals  are  obtained.  (CHHg). 
It  sinters  and  starts  to  decompose  at  65°.  At  125°  it  decomposes  very 
rapidly.  It  is  easily  soluble  in  alcohol,  chloroform,  acetone,  and  ethyl 
acetate,  fairly  soluble  in  warm  water,  ether,  benzene,  less  soluble  in 
cold  water,  and  hardly  at  all  in  ligroin. 

The  ester  can  be  changed  to  ethyl  formate  by  treatment  with  two 
equivalents  of  aluminum  activated  by  mercuric  chloride.  A  water 
solution  is  used.  The  reaction  takes  about  two  hours.  During  this 
time  the  mixture  must  be  kept  cold  or  some  carbon  monoxide  will  be 
liberated.  This  peculiar  formation  of  carbon  monoxide  would  favor 
the  conception  of  the  compound  as  a  loose  molecular  addition  product. 
When  the  reaction  is  complete  the  mixture  is  warmed  to  50°  and  hy- 
drogen is  blown  through  it.  The  escaping  vapors  are  passed  through 
tubes  cooled  in  a  Dewar  cylinder  containing  solid  carbon  dioxide  and 
ether.  An  80  per  cent  yield  of  pure  ethyl  formate  boiling  at  54.5°  is 
obtained.  The  calculated  amount  of  metallic  mercury  is  formed. 


MERCURY  DERIVATIVES  OF  FATTY  ACIDS          139 

Chloromercuriformic  methyl  ester. 

The  acetate  dissolved  in  methyl  alcohol  is  treated  with  a  solution 
of  sodium  chloride.  Long  white  needles  are  formed.  (CHClHg).  Yield 
80  per  cent.  On  rapid  heating  it  sinters  and  decomposes  at  109°  but 
gives  no  melting  point.  It  is  easily  soluble  in  acetone,  ethyl  acetate, 
chloroform,  and  alcohol,  fairly  soluble  in  warm  water,  benzene,  and 
ether,  less  soluble  in  cold  water,  and  very  little  soluble  in  ligroin. 

When  the  chloride  is  suspended  in  ether  it  decolorizes  iodine  and 
goes  into  solution.  Some  mercuric  iodide  separates.  A  strong  odor  of 
a  halogen  formic  ester  is  noticeable.  The  solution  is  cooled  and  am- 
monia is  passed  in.  Ammonium  chloride  is  filtered  off,  the  filtrate  is 
treated  with  hydrogen  sulfide  to  remove  all  mercury,  and  the  mixture 
is  again  filtered.  Evaporation  of  the  filtrate  leaves  an  oily  residue 
which  solidifies  on  cooling  and  can  be  recrystallized  from  low  boiling 
ligroin.  It  is  proved  to  be  methyl  urethane  by  its  melting  point  of  52° 
and  analyses  for  C,  H,  and  N.  Yield  68  per  cent. 

Chloromercuriformic  ethyl  ester. 

It  is  prepared  in  the  same  way  as  the  methyl  compound.  It  is 
recrystallized  from  warm  water  and  alcohol.  (CHClHg) .  It  melts  with 
decomposition  at  87°  (88°  corr.).  It  is  soluble  in  ethyl  acetate,  ace- 
tone, chloroform,  less  easily  in  water,  ether,  very  difficultly  in  low 
boiling  ligroin.  Treatment  with  iodine  in  ether  and  then  with  ammonia 
gives  a  70  per  cent  yield  of  ethyl  urethane  melting  at  50°  (N). 

When  the  chloride  is  heated  with  n-propyl  iodide  at  100°  -a  large 
amount  of  carbon  monoxide  is  formed.  No  ethyl  butyrate  is  ob- 
tained. This  result  is  not  surprising  as  organic  mercury  compounds 
do  not  react  with  alkyl  iodides  to  give  a  lengthened  carbon  chain. 

Bromomercuriformic  methyl  ester. 

It  is  prepared  from  the  acetate  in  the  usual  way.  It  is  best  re- 
crystallized  from  ether.  (CHBrHg).  It  decomposes  127-8°  with  evo- 
lution of  gas.  With  hydrochloric  acid  it  gives  carbon  monoxide.  The 
corresponding  ethyl  compound  is  similarly  prepared. 

lodomercuriformic  methyl  ester. 

It  is  prepared  like  the  chloride.  It  can  be  crystallized  from  ether 
in  leafy  .crystals  which  are  very  unstable.  (CHIHg).  The  crystals 
turn  yellow  on  standing  and  finally  decompose  entirely  giving  mercur- 
ous  iodide.  The  ethyl  compound  has  been  prepared. 


140  COMPOUNDS  OF  MERCURY 

Sulfide-mercuriformic  methyl  ester,  (CH302C  —  Hg — )2S. 

A  cold  saturated  methyl  alcohol  solution  of  the  acetate  is  treated 
at  0°  with  slightly  less  than  the  calculated  amount  of  a  titrated  solu- 
tion of  hydrogen  sulfide.  Any  excess  causes  decomposition  with 
evolution  of  carbon  monoxide.  The  product  is  a  white  cheesy  precipi- 
tate. (CHgHg) .  It  is  insoluble  in  all  solvents.  It  is  unstable,  readily 
giving  mercuric  sulfide. 

Other  compounds  have  been  made  which  may  be  regarded  as  mer- 
curated  formic  esters.2  They  are  obtained  by  the  oxidation  of  hydra- 
zine  carboxylic  esters  with  mercuric  oxide  and  have  the  general  formula, 

R02C  —  N  —  Hg  —  C02R.  Bromine  in  benzene  solution  forms  mer- 
R02C  —  N  —  Hg  —  C02R 

curie  bromide,  azodicarboxylic  ester,  R02C  —  N  =N  —  C02R,  and 
bromoformic  ester  which  is  identified  by  changing  it  to  the  correspond- 
ing urethane.  Treatment  with  piperidine  gives  metallic  mercury,  hy- 
drazodicarboxylic  ester,  R02C  —  NH —  NH —  C02R,  and  "piperyl- 
urethane,"  C5H10  =  N  —  C02R.  The  most  interesting  reaction  of  these 
substances  is  that  with  hydrochloric  acid  which  gives  a  quantitative 
yield  of  carbon  monoxide.  The  other  products  are  alcohol,  mercuric 
chloride,  and  hydrazodicarboxylic  ester.  This  reaction  shows  that  the 
grouping  —  Hg  —  C02R  is  peculiar  in  its  reaction  with  acids. 

The  ethyl  ester,  (C2H502C)2N2(Hg  — C02C2H5)2,  is  prepared  by 
treating  the  ethyl  ester  of  hydrazine  monocarboxylic  acid  with  a  sus- 
pension of  freshly  prepared  pure  mercuric  oxide.  A  considerable 
amount  of  gas  is  evolved.  This  consists  of  nitrogen  with  traces  of 
carbon  monoxide  and  a  compound  which  is  probably  an  organic  azide. 
The  solid  residue  contains  mercury  and  the  product.  The  latter  is 
extracted  with  boiling  water.  Yield  5  gm.  of  the  mercury  compound 
from  30  grams  of  the  original  ester.  It  is  recrystallized  from  a  small 
amount  of  hot  benzene  or  toluene.  M.P.  155°.  (CHNHg,  M.W.  by 
B.P.)  The  original  reaction  also  gives  hydrazodicarboxylic  ethyl 
ester. 

The  formation  of  this  substance  from  hydrazine  carboxylic  ester 
bears  a  close  relation  to  the  reactions  by  which  Emil  Fischer  obtained 

'Diels  and  Uthemann,  Ber.  53  (1920),  723. 


MERCURY  DERIVATIVES  OF  FATTY  ACIDS          141 

mercury  diethyl  and  mercury  diphenyl  during  the  oxidation  of  ethyl 
hydrazine  and  phenyl  hydrazine  by  mercuric  oxide.3 

The  corresponding  methyl  ester  is  prepared  in  the  same  way  as  the 
ethyl  compound  and  has  similar  properties.  M.P.  215°.  (CHNHg). 

Mercurated  Acetic  Acids.4 

Bromomercuri-acetic  acid,  BrHg  —  CH2C02H. 

Bromine  and  potassium  hydroxide  are  allowed  to  react  on  a  methyl 
alcohol  solution  of  ethanol  mercuric  bromide,  HOCH2  —  CH2  —  HgBr, 
obtained  from  the  reaction  product  of  ethylene  and  basic  mercuric  ni- 
trate. The  mercurated  acetic  acid  forms  a  white  crystalline  precipitate. 
(CHBrHg).  M.P.  198°.  When  a  solution  in  potassium  cyanide  is 
treated  with  hydrogen  sulfide  mercuric  sulfide  is  obtained  at  once. 
The  filtrate  is  evaporated  to  dryness  and  the  residue  is  extracted  with 
absolute  alcohol  to  extract  the  potassium  acetate.  This  is  identified 
by  changing  to  silver  acetate. 

Potassium  iodide  reacts  with  bromomercuri  acetic  acid  giving  a 
yellow  iodide  which  is  not  changed  by  20  per  cent  nitric  acid,  dilute 
hydrochloric  acid,  or  ammonium  hydroxide. 

Anhydro  hydroxymercuri-acetic  acid.5 

Mercuric  acetate  heated  above  its  melting  point  gives  a  compound 
which  is  probably  a  mercurated  acetic  acid  or  an  anhydride  of  such  a 
substance. 

A  substance  which  is  probably  a  trimolecular  form  of  this  an- 
hydride is  obtained  by  treating  mercury  malonic  ester  with  sodium 
hydroxide  for  some  time  at  37°  and  then  precipitating  with  carbon 
dioxide.6  (CHHg) .  Yield  90  per  cent.  It  decomposes  at  250°  with 
a  slight  explosion.  Probably  the  same  substance  is  obtained  by  treat- 
ing malonic  acid  with  an  excess  of  sodium  hydroxide  and  precipitated 
mercuric  oxide.  The  evidence  for  the  trimolecular  formula  is  that 
one  molecule  of  formic  acid  reacts  with  an  amount  of  the  anhydride 

»E.  Fischer,  Ann.  199   (1879),  332. 

*  Hofmann  and  Sand,  Ber.  33  (1900),  1340.  Sand,  Ber.  34  (1901),  1385.  Dim- 
roth,  Ber.  35  (1902),  2853.  Sand  and  Genssler,  Ber.  36  (1903),  3699.  Schoeller 
and  Schrauth,  Ber.  41  (1908),  2087.  Biilmann,  Ber.  42  (1909),  1068.  Schoeller  and 
Schrauth,  D.  R.  P.  219,  966.  Chem.  Zentr.  1910  I  1078. 

6Dimroth,  loc.  cit.  2870. 

"Schoejler  and  Schrauth,  Ber.  41   (1908),  2090, 


142  COMPOUNDS  OF  MERCURY 

corresponding  to  three  of  the  single  molecules,  CH2  —  C  =  0.     Thus 

Hg  — 0 

the  trimolecular  anhydride  would  be  CH2  —  CO  —  OHg  —  CH2.    The 

Hg  CO 

0  — CO  — CH2  — HgO 

product  obtained  by  dissolving  this  in  formic  acid  and  precipitating  by 
alcohol  would  have  the  formula,  HC02Hg  —  CH2  —  C02Hg  —  CH2  - 
C02Hg  — CH2  — C02H.      (CHHg).     Yield  70  per   cent.     Colorless 
crystals  decomposed  by  heat.    It  is  insoluble  in  all  common  solvents. 

A  difference  of  opinion  exists  as  to  the  possibility  of  making  the 
above  anhydride  from  malonic  acid,  sodium  hydroxide,  and  mercuric 
oxide.  Biilmann  carried  out  the  reaction  between  these  substances 
using  four  different  sets  of  conditions.7  He  believes  the  product  to 

C02H   . 
/ 
C02Hg  — C  — CO 

/  \      \ 

have  the  complex  structure,  Hg  —  C  Hg  —  0     (CHHg) . 

\ 

C02Hg  — C  — C02H 

CO 


Sodium  salt  of  hydroxymercuri-acetic  acid,  HOHg  —  CH2C02Na. 8 

The  anhydride  obtained  from  mercury  malonic  ester  is  dissolved 
in  one  molecule  of  sodium  hydroxide  for  each  atom  of  mercury  and 
evaporated  with  the  exclusion  of  carbon  dioxide.  The  substance  is  ob- 
tained in  small  needles  soluble  in  water  but  insoluble  in  organic  sol- 
vents: Ammonium  sulfide  gives  mercuric  sulfide.  Metallic  copper 
gives  no  action.  The  solution  of  the  sodium  salt  does  not  coagulate 
albumen.  Heavy  metal  salts  may  be  prepared  by  precipitation.  Thus 
the  copper  salt  is  made  by  mixing  solutions  of  the  sodium  compound 
and  copper  sulfate.  (Cu). 

7  Ber.  42   (1909),  1068. 
81:>choeller  and  Schrauth,  loc.  ci£. 


MERCURY  DERIVATIVES  OF  FATTY  ACIDS          143 

Nitratemer curl-acetic  acid,  NO3  —  Hg  —  CH.,C02H. 

The  anhydride  dissolves  in  fairly  concentrated  nitric  acid  and  gives 
a  precipitate  of  variable  composition  when  treated  with  water  or 
alcohol. 

C hloromercuri-acetic  acid.9 

A  double  compound  of  the  potassium  salt  with  potassium  chloride 
is  obtained  by  boiling  potassium  monochloroacetate  with  mercuric 
oxide  and  water.  It  can  be  crystallized  from  alcohol.  White  matted 
needles.  (CHClKHg).  Dilute  hydrochloric  acid  immediately  gives 
mercuric  chloride,  potassium  chloride,  and  glycollic  acid.  Sodium  hy- 
droxide precipitates  mercuric  oxide.  This  reaction  is  most  unusual 
for  a  carbon  mercury  compound.  It  does  not  reduce  ammoniacal  silver 
solution. 

Mercuri-nitratemercuri-acetic  acid,  Hg  =  C  —  C02H  10 


tg  — NO.. 

Sodium  acetate,  yellow  mercuric  oxide,  and  concentrated  potassium 
hydroxide  are  heated  on  the  steam  bath  until  the  oxide  disappears. 
The  yellowish  white  solid  is  extracted  with  hot  water  and  washed  with 
5  per  cent  potassium  hydroxide.  The  solution  contains  the  potassium 
salt  of  mercuri-hydroxymercuri-acetic  acid,  Hg  =  C  —  C02H.  The 

Hg  — OH 

insoluble  substance  is  probably  a  polymer  of  this  acid.  It  is  dissolved 
in  30  per  cent  nitric  acid  and  precipitated  by  water.  The  nitrate  forms 
a  yellowish  white  crystalline  substance.  (CHHg).  It  decomposes  on 
heating.  Hot  dilute  hydrochloric  acid  dissolves  it  with  partial  decom- 
position. 10  per  cent  potassium  cyanide  gives  a  solution  of  mercuric 
cyanide  and  potassium  acetate.  Sodium  carbonate  and  even  5  per  cent 
potassium  hydroxide  replace  the  nitrate  group  by  hydroxyl  without  re- 
acting with  the  carboxyl  group.  The  product  is  a  bluish  white  precipi- 
tate of  Hg  =  C  —  C02H.  Only  a  large  excess  of  a  base  will  dissolve 

Hg  — OH 

the  precipitate  forming  a  salt. 

•  Hofmann,  Ber.  32   (1899),  880 

875. 


144  COMPOUNDS  OF  MERCURY 

Potassium  salt  of  mercuri-hydroxymercuri-acetic  acid, 
Hg  =  C  —  C02K.Hg  =  C  —  C02H.2H20. 

HgOH  HgOH 

The  solution  in  5  per  cent  potassium  hydroxide  obtained  during 
the  preparation  of  the  above  nitrate  is  precipitated  by  dilute  nitric 
acid  as  a  bright  yellow  jelly.  This  is  dissolved  in  5  per  cent  potassium 
hydroxide  using  a  large  excess  to  avoid  the  formation  of  the  insoluble 
polymer.  The  solution  is  treated  with  methyl  or  ethyl  alcohol  which 
gives  a  yellow  precipitate  of  the  acid  potassium  salt.  (CHKHg,H20). 

Dichloromercuri-acetic  acid  (ClHg)2CH  —  C02H. 

The  above  potassium  salt  is  treated  with  2  per  cent  hydrochloric 
acid  or  the  original  solution  in  5  per  cent  potassium  hydroxide  is 
treated  with  an  excess  of  dilute  hydrochloric  acid.  (CHClHg) . 

Mercuri-hydroxymercuri-acetic  acid}  Hg  =  C  —  CO,,!!.11 


[g-OH 

The  corresponding  nitrate  is  boiled  with  sodium  carbonate  solution. 
Another  preparation  starts  with  ethanol  mercuric  iodide,  CH2OH  — 
CH2  —  Hgl,  obtained  from  ethylene  and  mercuric  salts.  This  is  boiled 
with  potassium  hydroxide  and  mercuric  oxide.  The  residue  is  dis- 
solved in  20  per  cent  nitric  acid,  filtered,  and  precipitated  by  water. 
The  precipitate  is  washed  with  2  per  cent  nitric  acid  and  then  boiled 
with  an  excess  of  sodium  carbonate  solution  to  form  the  desired  acid. 
(CHHg). 

As  has  been  mentioned  an  insoluble  polymer  of  this  acid  is  formed 
in  the  reaction  between  sodium  acetate  and  mercuric  oxide  in  alkali. 
It  remains  after  the  extraction  with  5  per  cent  potassium  hydroxide. 
It  dissolves  in  concentrated  potassium  hydroxide  only  on  long  boiling. 

Trichloromercuri- acetic  acid,  (ClHg)3C  —  C02H.12 

This  substance  may  be  prepared  from  monochloroacetylene  and  mer- 
curic chloride.  It  may  also  be  made  from  the  mercarbide,  C2Hg4Cl4, 
obtained  from  sodium  acetate  and  alcoholic  mercuric  chloride.13  When 
this  is  heated  with  sodium  hydroxide  and  the  solution  is  precipitated 
with  dilute  hydrochloric  acid  the  trichloromercuri-acetic  acid  is  ob- 

11  Hofmann  and  Sand,  Ber.  33   (1900),  1348. 

12  Hofmann,  Ber.  31   (1898),  2217.     Hofmann,  Ber.  32  (1899),  872.     Hofmann  and 
Kirmreuther,  Ber.  42    (1909),  4234, 

11  Hofmann,  Joe.  cit. 


MERCURY  DERIVATIVES  OF  FATTY  ACIDS          145 

tained  as  a  white  amorphous  solid.    (ClHg).  The  residue  insoluble  in 
the  base  contains  the  explosive  ethane  hexamercarbide. 

Anhydride  of  Hydroxymercuri-diacetoxymercwri-acetic  acid, 
(AcOHg)2C  —  C  =  0.  14 


U 


g 

Dry  mercuric  acetate  is  heated  with  freshly  distilled  acetic  anhy- 
dride until  a  portion  tested  with  sodium  hydroxide  gives  no  mercuric 
oxide.  A  fine  microcrystalline  precipitate  is  obtained.  (CHHg).  It  is 
insoluble  in  organic  solvents,  soluble  with  decomposition  in  hydro- 
chloric acid  and  potassium  cyanide,  but  soluble  without  decomposition 
in  20  per  cent  nitric  acid.  The  hydroxide  and  iodide  are  prepared 
by  potassium  hydroxide  and  potassium  iodide  respectively. 

Anhydride     of     hydroxymercuri-acetoxymercuri-nitratemercuri-acetic 
acid,    AcO  — Hgx^      /HgO 

C      / 

N03  —  Hgx     ^C=0 

This  substance  is  prepared  by  dissolving  the  above  acetate  in  20 
per  cent  nitric  acid  and  diluting  with  water.  (CHNHg) .  Its  properties 
are  like  those  of  the  acetate. 

Trihydroxymercuri-acetic  acid.*5 

The  acetate  obtained  from  mercuric  acetate  and  acetic  anhydride 
is  treated  with  cold  10  per  cent  potassium  hydroxide.  The  solid  prod- 
uct is  washed  with  dilute  alkali,  water,  and  alcohol.  It  explodes  if 
heated  to  about  200°.  It  is  readily  soluble  in  cold  20  per  cent  hydro- 
chloric acid  and  in  potassium  cyanide  solution.  If  heated  at  160°  it 
gives  a  loss  corresponding  to  2.5  molecules  of  water  and  one  of  carbon 
dioxide.  The  original  substance  thus  contains  water  of  crystallization. 

When  the  acid  is  warmed  with  water  and  sodium  amalgam  for  two 
hours,  saturated  with  carbon  dioxide,  and  evaporated  to  dryness  a 
residue  is  left  from  which  alcohol  extracts  sodium  acetate.  This  is 
identified  by  changing  to  the  silver  salt. 

Anhydride  of  hydroxymercuri-di-iodomercuri-acetic  acid.  (?) 

The  above  trimercurated  acid  is  treated  with  potassium  iodide. 
(No  analyses)  Treatment  of  the  iodine  compound  with  alcohol  and 
iodine  gives  iodoform  and  mercuric  iodide. 

"Sand  and  Genssler,  Ber.  36   (1903),  3707. 
»/6fd.  3708. 


146  COMPOUNDS  OF  MERCURY 

Sodium  salt  of  dihydroxymercuri-iodomer curl-acetic  acid, 
HO  — Hg  HgOH.    16 

\    / 
C 

/    \ 

I  — Hg  C02Na 

Sodium  acetate  is  heated  with  sodium  hydroxide  and  mercuric 
iodide  at  105°.  The  yellow  leaflets  of  the  sodium  salt  are  purified  by 
repeated  extractions  with  hot  dilute  alkali.  (CINaHg).  The  sub- 
stance is  only  slightly  decomposed  by  hot  dilute  hydrochloric  acid  or 
bromine  water.  It  is  decomposed  by  potassium  cyanide  solution.  The 
free  acid  is  obtained  from  the  sodium  salt  by  treatment  with  dilute 
nitric  acid.  It  forms  greenish  white  leaflets.  (CHIHg).  Treatment 
of  the  acid  with  hot  potassium  iodide  gives  an  alkaline  solution. 

Dihydroxymercuri-nitratemercuri-acetic  acid, 

HO  — Hg  Hg  — OH    " 

\     / 
C 

/     \ 
N03  —  Hg  C02H 

The  above  iodide  is  treated  with  a  hot  dilute  silver  nitrate  solu- 
tion. The  solid  product  is  extracted  with  30  per  cent  nitric  acid  which 
leaves  the  silver  iodide.  The  solution  is  diluted.  The  yellowish  white 
precipitate  is  purified  by  dissolving  again  in  nitric  acid  and  precipitat- 
ing by  water.  (CHNHg).  It  decomposes  on  heating.  It  is  soluble  with 
partial  decomposition  in  hydrochloric  acid,  potassium  cyanide,  and 
potassium  iodide. 

Mercurated  Propionic  Acids. 

Anhydride  of  a-hydroxymercuripropionic  acid,  CH3  —  CH  —  C  =  O.18 

Hg  — 0 

Hydroxymercuri  methyl  malonic  methyl  ester  is  boiled  a  short  time 
with  2.5  moles  of  normal  sodium  hydroxide.  A  slight  precipitate  is 
filtered  off  and  the  filtrate  is  treated  with  a  slight  excess  of  normal  sul- 

"Hofmann,  Ber.  32   (1899),  878. 
» Ibid. 

"Schoeller   and    Schrauth,    Ber.    42    (1909),    782.      Chem.   Zentr.    1909    I    1520. 
Chem.  Abet.  4  (1911),  3018. 


MERCURY  DERIVATIVES  OF  FATTY  ACIDS          147 

furic  acid.  The  precipitate  which  forms  is  filtered,  washed,  and  sus- 
pended in  water.  The  mixture  is  then  boiled  until  no  more  carbon 
dioxide  escapes.  The  product  is  an  amorphous  powder.  (CHHg). 
Yield  97  per  cent.  Heating  to  150°  causes  decomposition  with  the 
formation  of  mercury  and  carbon.  Halogen  acids  decompose  it  giving 
mercuric  halides.  Dilute  sulfuric  acid  has  no  effect.  Dilute  nitric 
acid  gives  nitrates  of  the  mercurated  propionic  acid  of  varying  com- 
position. The  anhydride  is  insoluble  in  organic  solvents  but  is  easily 
soluble  in  alkalies  giving  the  corresponding  salts  of  a-hydroxymercuri 
propionic  acid.  The  acid  properties  are  too  weak  for  it  to  form  salts 
with  alkaloids  which  might  be  used  for  its  separation  into  optical 
isomers.  The  C  —  Hg  linkage  in  this  compound  is  unusually  unstable 
to  acids. 

^-Mercury  bis-propionic  acid,  Hg(CH2  —  CH2  —  C02H)2. 19 

|3-Iodopropionic  ethyl  ester  is  treated  with  0.5  per  cent  sodium  amal- 
gam and  ether  in  the  cold.  The  ether  solution  is  separated  and  evapo- 
rated leaving  a  yellow  oil.  This  is  shaken  with  normal  sodium  hy- 
droxide and  warmed.  The  solution  is  cooled  and  treated  with  a  slight 
excess  of  dilute  sulfuric  acid.  Colorless  crystals  separate.  Yield  27 
per  cent.  It  is  quickly  crystallized  from  a  large  volume  of  hot  water. 
(CHHg).  M.P.  147-8°  (corr.  148.5-149.5°),  with  darkening.  It  is 
easily  soluble  in  warm  alcohol,  fairly  soluble  in  hot  ethyl  acetate  and 
acetone,  difficultly  soluble  in  ether  and  chloroform.  It  neutralizes  two 
equivalents  of  sodium  hydroxide  with  phenolphthalein  as  an  indicator. 
It  forms  salts  readily.  The  silver  salt  is  made  by  treating  a  solution  of 
the  sodium  salt  with  silver  nitrate. 

If  a  water  solution  of  the  acid  is  warmed  gently  with  iodine  in 
potassium  iodide  solution  it  gives  a  dark  crystalline  precipitate  which 
appears  to  be  a  periodide. 

Treatment  with  hot  concentrated  hydrobromic  acid  gives  a  solu- 
tion which  deposits  crystals  on  cooling.  These  may  be  |3-bromomer- 
curipropionic  acid,  BrHg  —  CH2  —  CH2  —  C02H. 

If  the  acid  is  heated  with  water  at  100°  it  forms  propionic  acid  and 
the  anhydride  of  fi-hydroxymercuripropionic  acid,  CH2  —  CH2. 

/  \ 

Hg  — 0  — CO 
(CHHg).    This  is  almost  insoluble  in  water  and  common  solvents.    It 

"Emil  Fischer,  Ber.  40   (1907),  387. 


148  COMPOUNDS  OF  MERCURY 

is  easily  soluble  in  alkalies  and  in  warm  dilute  mineral  acids.    It  turns 
gray  and  decomposes  at  190°. 

Butyric  acid  has  been  mercurated.20 

Mercurated  Nitroacetic  Ester.21 

Anhydride  of  hydroxymercuri  aci-nitroacetic  ethyl  ester, 

Hg  — 0 

/ 


C  = 


\ 
C02C2H5. 

The  ammonium  compound  of  aci-nitroacetic  ethyl  ester  is  dissolved 
in  water  and  treated  with  mercuric  chloride  solution.  The  product  pre- 
cipitates slowly.  (Hg)  .  It  is  insoluble  in  boiling  water  but  soluble  in 
base  solutions.  Dilute  hydrochloric  acid  dissolves  it  without  forming 
any  nitroacetic  ester.  The  product  is  probably  chloromercurinitro- 

HgCl 
/ 

acetic  ester,  CH  —  N02.     An  excess  of  acid  removes  the  mercury. 
\ 
C02Et 

The  solution  in  sodium  hydroxide  probably  contains  the  sodium  aci- 

HgOH 
/ 

nitro  derivative,  C  =  N02Na.    Bromine  in  potassium  bromide  solution 
\ 
C02Et 

gives  dibromonitroacetic  ester.  (Br).  Potassium  iodide  removes  the 
mercury  as  mercuric  iodide  indicating  that  the  mercury  is  very  loosely 
attached  to  the  carbon. 

Mercury  Compounds  from  Unsaturated  Acids.22 

The  following  unsaturated  acids  give  C  —  Hg  compounds  on  treat- 
ment with  mercuric  salts:  acrylic,  crotonic,  maleic,  itaconic,  citraconic, 
and  allocinnamic.  The  product  contains  the  groups  —  HgX  and 

20Schoeller  and  Schrauth,  Ghent  Zentr.  1910  I  1678.  Chem.  Afat.  4  (1911), 
3015,  3018. 

21Prager,  Monatsh.  33   (1912),  1286. 

22  Biilmann,  Ber.  35  (1902),  2571.  D.  R.  P.  228,877  Fraenkel,  Arzneimittel- 
synthese,  4th  Ed.  666. 


MERCURY  DERIVATIVES  OF  FATTY  ACIDS          149 

—  OH  added  to  the  double  bond  of  the  original  molecule.  No  mercury 
compounds  are  given  by  the  transisomers  such  as  cinnamic,  mesaconic, 
and  fumaric  acids.  Esters  of  unsaturated  acids  such  as  methyl  cinna- 
mate,  ethyl  oleate,  triolein,  and  lecithin  give  mercury  compounds 
when  treated  with  mercuric  salts  in  alcohol.  In  this  case  the  groups 
added  are  —  HgX  and  —  OR.  In  the  a-(3  unsaturated  acids  and  esters 
the  mercuri  group  takes  the  a  position.  Treatment  with  alkali  and 
then  with  sulfuric  acid  gives  anhydrides  or  inner  salts  containing  the 
grouping  =  C  —  C  =  0.  These  anhydrides  are  soluble  in  acids,  bases, 

I         I 
Hg-0 
and  alkaline  carbonates  giving  salts  of  the  types  =  C  —  C02H  and 


[gX 

=  C  —  C02M. 

HgOH 

Anhydride  of  a-hydroxymercuri-fi-hydroxypropionic  acid, 

CH2  —  CH  —  C  =  0. 


OH       Hg  — O 


Hg 

Acrylic  acid  is  treated  with  an  acid  solution  of  mercuric  sulfate. 
When  alcohol  is  added  to  the  mixture  a  white  smeary  precipitate  re- 
sults. Longer  treatment  with  alcohol  renders  this  granular  and  suit- 
able for  filtration.  It  is  very  hygroscopic.  It  appears  to  have  the 
formula  C12H18012Hg4(S04).  If  boiled  with  water  it  gives  a  soluble 
sulfate  and  the  anhydride.  (CHHg) . 

The  anhydride  can  also  be  made  by  boiling  one  molecule  of  yellow 
mercuric  oxide  with  acrylic  acid.  When  the  anhydride  is  treated  with 
potassium  iodide  about  one  equivalent  of  potassium  hydroxide  is 
formed.  This  indicates  that  the  C  —  Hg  linkage  is  very  easily  broken 
in  this  case.  The  anhydride  is  very  slightly  soluble  in  water  even  on 
heating.  It  is  easily  soluble  in  acids,  alkalies,  and  alkali  carbon- 
ates. Ammonium  hydroxide  and  ammonium  sulfide  give  mercuric  sul- 
fide.  Sodium  chloride  and  ammonium  chloride  dissolve  the  anhydride 
without  giving  an  alkaline  solution.  These  solutions  probably  con- 
tain salts  of  the  type  CH2OH  —  CH  —  C02Na.  A  chloride  solution 


does  not  split  the  C  —  Hg  linkage  as  does  an  iodide  solution.23 

23Whitmore  and  Middleton,  J.  Am.  Chem.  Soc.  43   (1921),  619. 


150  COMPOUNDS  OF  MERCURY 

Still  another  method  for  making  the  anhydride  is  to  heat  mer- 
curous  acrylate  forming  metallic  mercury,  acrylic  acid,  and  the  an- 
hydride. 

Anhydride  of  a-hydroxymercuri-fi-hydroxy-n-butyric  acid, 
CH3  —  CHOH  —  CH  —  C  =  0. 24 


L-i, 


Crotonic  acid  is  warmed  with  mercuric  acetate  solution  and  a  trace 
of  acetic  acid,  cooled,  and  precipitated  by  alcohol.  The  anhydride 
can  also  be  made  by  boiling  crotonic  acid  solution  with  mercuric 
oxide  until  the  product  is  completely  soluble  in  sodium  hydroxide. 

If  the  anhydride  is  dissolved  in  normal  sodium  hydroxide,  treated 
with  hydrogen  sulfide,  and  then  acidified  with  sulfuric  acid  and  filtered 
a  solution  is  obtained  from  which  an  oil  can  be  extracted  by  ether. 
This  oil  is  not  crotonic  acid  but  gives  that  substance  when  boiled  with 
50  per  cent  sulfuric  acid.  It  is  therefore  (3-hydroxybutyric  acid  formed 
by  the  replacement  of  the  mercury  by  hydrogen. 

Mercury  derivatives  of  other  unsaturated  acids. 
Oleic  acid.25 
Chaulmoogra  oil  and  its  esters.26 

Mercuric  salt  of  a-acetoxymercuri-fi-hydroxy  succinic  acid, 

AcOHg  — CH  — C02 
\ 
Hg.2H20. 27 

HO  — CH  — C02 

A  water  solution  of  maleic  acid  gives  a  slight  yellow  precipitate. 
This  is  heated  with  more  maleic  acid  forming  white  crystals.  (CHHg) . 
It  is  insoluble  in  water  and  alcohol,  soluble  in  acids,  even  in  acetic 
acid  if  not  too  dilute.  It  is  soluble  in  alkalies  with  the  precipitation 
of  part  of  the  mercury  as  the  oxide.  Sodium  chloride  dissolves  it  with 
a  slight  acid  reaction.  Potassium  iodide  dissolves  it  with  the  formation 
of  almost  exactly  one  equivalent  of  base  indicating  the  splitting  of 

24  Ley,   Ber.   33    (1900),   1014.      Biilmann,  Ber.   35    (1902),   2572.      Ley,   Bull.   soc. 
chim.   (3)  33  (1905),  1320.     Biilmann,  Ber.  43   (1910),  579. 

25  Fraenkel,  Arzneimittelsynthese,  4th  Ed.  1919,  666  ff.     RealemyJc.  Pharm.  VI  494. 
Leys,   J.   pharm.   chim.    (6)    21    (1905),   388.      Ohem.    Zentr.    1905    I   1532.      Schoeller, 
Schrauth,  and  Struensee,  Ber.  43   (1910),  695. 

26  D.  R.  P.  245,  571.     Fraenkel,  loc.  cit. 

27  Biilmann,  loc.  cit.     Ley,  loc.  cit. 


MERCURY  DERIVATIVES  OF  FATTY  ACIDS          151 

the  C  —  Hg  linkage.  Treatment  with  sodium  hydroxide  and  hydrogen 
sulfide  gives  a  solution  from  which  malic  acid  can  be  extracted  in  80 
per  cent  yield.  Fumaric  acid  when  treated  with  mercuric  salts  gives 
only  an  ordinary  0  —  Hg  compound. 

Mercury   salt    of   a-acetoxymercuri-ft-hydroxy- ft  (1) -methyl    succinic 
CH3 

AcOHg  — C  — C02 
acid,  Hg.3H20. 

HO  —  C  —  CO, 


Citraconic  acid  is  heated  with  mercuric  acetate  at  60°  forming  a 
white  crystalline  precipitate.  (CHHg).  The  product  is  insoluble  in 
water  and  alcohol  but  soluble  in  acids.  Bases  precipitate  part  of  the 
mercury  as  the  oxide.  The  alkaline  solution  contains  the  rest  of  the 
mercury  which  can  be  precipitated  by  hydrogen  sulfide.  Potassium 
iodide  does  not  split  the  C  —  Hg  linkage  completely  as  it  gives  only  .8 
of  an  equivalent  of  alkali.  Mesaconic  acid  gives  only  common  mer- 
curic salts  from  which  bases  precipitate  all  of  the  mercury. 

Mercury  salt  of  anhydro-a-hydroxymercuri-a-hydroxy methyl  succinic 
C  =  0 

/    \ 

acid,  HO  —  CH2  —  C  —  HgO 


L2  — C02hg.  2 

Itaconic  acid  reacts  with  mercuric  sulfate  solution  and  alcohol  to 
form  a  complex  sulfate  which  changes  to  the  desired  compound  on 
boiling  with  water.  The  product  is  a  white  insoluble  substance  contain- 
ing 3H20.  (CHHg).  It  is  easily  soluble  in  acids  and  in  solutions  of 
halide  salts.  Potassium  iodide  breaks  the  C  —  Hg  linkage. 

Acetylenic  acids  and  esters  give  mercury  compounds  in  much  the 
same  way  as  the  ethylene  compounds.29 

Hydroxy  acids  such  as  lactic,  malic,  and  tartaric  acids  give  ordinary 
0  —  Hg  Salts.30 

28  The  symbol  "hg"  is  used  to  indicate  one  equivalent  of  mercury. 

29  Ley,  Ber.  33  (1900),  1014.     D.  R.  P.  246,  207.     Fraenkel,  loc.  cit.  667. 
30Engelhardt  and  Maddrell,  Ann.  63   (1847),  95.     Bruning,  Ann.  104   (1857),  194. 

Balestra,   Chem.  Zentr.  1893  I   559.      Gmelin-Kraut-Friedheim-Peters  Handbuch.   V,   II 
454.     Merck's  Index,  1907,  282. 


152  COMPOUNDS  OF  MERCURY 

Mercury  Derivatives  of  Keto  Acids. 

Acetoacetic  ester  gives  mercury  compounds  to  which  a  variety  of 
formulas  has  been  assigned.31  None  of  these  is  conclusively  proved. 
The  compounds  are  decomposed  by  concentrated  acids  and  potassium 
cyanide  solution.  Hydrogen  sulfide  gives  mercuric  sulfide  at  once. 
Their  properties  indicate  the  presence  of  a  very  weak  C  —  Hg  bond 
such  as  is  always  found  when  the  carbon  involved  is  alpha  to  a  car- 
boxyl  or  carbonyl  group. 

Other  keto  acids. 

Levulinic  acid  gives  ordinary  mercuric  salts.32 

Tartronic  acid.33 

Acetone  dicarboxylic  acid  gives  a  complex  mercury  compound 
which  may  very  likely  contain  some  organic  mercury.34 

Mercury  Derivatives  of  Malonic  Esters. 

Mercury  bis-malonic  methyl  ester  Hg[CH(C02CH3)2]2. 35 

Methyl  malonate  is  shaken  in  the  dark  with  water  and  freshly 
prepared  yellow  mercuric  oxide.  Yellow  aggregates  are  formed  first 
but  in  about  twelve  hours  the  product  is  entirely  white.  It  is  dissolved 
in  a  large  amount  of  cold  chloroform  and  ether  is  added  until  crystal- 
lization starts.  (CHHg).  It  softens  at  125°  and  melts  at  127°  corr. 
A  few  degrees  higher  it  solidifies  and  does  not  melt  again  but  decom- 
poses at  a  high  temperature.  The  crystals  are  slightly  soluble  in  cold 
alcohol,  ethyl  acetate,  and  acetone.  On  standing  or  warming  it 
changes  to  an  amorphous  insoluble  substance  which  is  insoluble  in 
chloroform  and  is  probably  a  polymer. 

Saponification  of  the  ester  and  acidification  with  sulfuric  acid  give 
the  trimolecular  anhydride  of  hydroxymercuri-acetic  acid. 

Sodium  malonate  when  heated  with  mercuric  oxide  and  alkali  forms 

81Lippmann,  Z.  Chem.  (2)  5  (1869),  29.  Oppenheim,  B&r.  10  (1877),  701. 
Behrend,  Z.  physik.  Chem.  11  (1893),  478.  Hofmann,  Ber.  31  (1898),  2215.  Ley, 
B&r.  33  (1900),  1014.  Biilmann,  Ber.  35  (1902),  2585.  Michael,  Ber.  38  (1905), 
2090. 

82  Ley,  Ber.  53  (1900),  1012. 

"Leys,  Bull.  soc.  cMm.  (3)   33  (1905),  1316. 

84Deniges,  Ann.  cMm.  phys.  (7)  18  (1899),  408  ff.  Ley,  Ber.  33  (1900),  1013. 
Deniges,  Ann.  chim.  phys.  (8)  12  (1907),  396. 

"Biilmann,  Ber.  35  (1902),  2580.  Schoeller  and  Schrautb,  Ber.  41  (1908),  2089; 
42  (1909),  778. 


MERCURY  DERIVATIVES  OF  FATTY  ACIDS          153 

an  organic  mercury  compound.    A  difference  of  opinion  exists  as  to 
the  exact  nature  of  this  substance.36 

Hydroxymercuri  methyl  malonic  methyl  ester, 

HOHg  —  C(CH*8)  (C02CH3)2. 

Equal  molecules  of  methyl  malonic  methyl  ester  and  fresh  mercuric 
oxide  are  shaken  in  the  dark  at  37°  for  several  days.  A  light  yellowish 
red  product  is  obtained.  This  product  contains  considerable  mercuric 
oxide  which  is  left  behind  on  saponifying  the  ester.  To  obtain  the 
pure  ester  the  mercuric  oxide  is  removed  by  thorough  washing  with  1 
per  cent  acetic  acid.  A  white  amorphous  solid  is  left  which  is  insoluble 
in  all  common  solvents.  The  ester  is  washed  thoroughly  and  dried 
in  vacuo.  (CH,Hg  high).  The  high  value  for  mercury  may  be  due  to 
partial  hydrolysis.  It  does  not  melt  but  darkens  and  decomposes  if 
heated  rapidly  to  235°.  It  is  soluble  in  dilute  acids  forming  salts  if 
an  excess  of  acid  is  avoided.  It  dissolves  in  bases.  Ammonium  sul- 
fide  blackens  it  at  once. 

Methyl  malonic  methyl  ester  reacts  with  mercuric  chloride  in  alco- 
hol giving  various  insoluble  products  including  one  which  is  regarded 
as  "chloro  dimercuri  methyl  malonic  ester." 

If  the  reaction  between  methyl  malonic  methyl  ester  and  mercuric 
oxide  is  carried  out  at  about  100°  acidification  of  the  solution  gives 
a-hydroxymercuripropionic  acid  in  80  per  cent  yield. 

The  malonic  ester  also  reacts  with  mercuric  acetate  or  mercury 
acetamide  giving  products  from  which  the  mercurated  propionic  acid 
derivative  can  be  obtained. 

Succinic  acid  gives  ordinary  mercuric  salts.37 

Aminomethane  disulfonic  acid  reacts  with  alkali  and  mercuric  oxide 
giving  mercury  compounds.38 

Citric  acid  gives  peculiar  mercury  compounds  which  have  not  been 
studied  carefully.39 

36  See  Mercurated  acetic  acids. 

"Doepping,  Aim.  47  (1843),  289.  Realenzyk.  Pharm.  VI  506.  Gmelin-Kravt- 
Friedhcim-Peters  Handbuch.  V-II  454.  Merck's  Index  1907  281. 

38  D.  R.  P.  279,  199.  Fraenkel,  Arzneimittelsynthese,  4th  Ed.  1919,  670.  Chem. 
Zentr.  1914  II  1175. 

"Vauquelin  (before  1832),  Gmelin-Kraut  Hanttuch,  4th  Ed.  1852  V  831.  Real' 
enzyk.  Pharm.  VI  481.  Chem.  Zentr.  1913  I  743. 


Chapter  VIII. 

Mercury  Derivatives  of  Aldehydes,  Ketones,  and  Acid 

Amides. 

Mercury  Aldehyde  Compounds. 

Almost  all  aldehydes  reduce  mercuric  acetate  to  the  mercurous 
compound  in  a  few  hours.1 

Acetaldehyde  reacts  with  mercuric  oxide  and  alkali  giving  a  sub- 
stance (C4H805Hg3)x  which  is  probably  a  polymer  of  a  compound, 

HOHg  — CH  — Hg  — CH  — HgOH.  2  (Hg). 

CHOH— 0— CHOH 

The  same  reagents  give  another  product  which  is  formulated  as  a 
mercury  compound  of  vinyl  alcohol,  (CH2  =  CH — )2Hg.Hg0.3 
(CHHg). 


Mercuri-chloratemercuri-acetaldehyde,  Hg  =  C  —  CHO.  * 

Hg-C103 

A  solution  of  basic  mercuric  chlorate  reacts  with  the  calculated 
amount  of  acetaldehyde  giving  colorless  sharp  ended  prisms.  The  sub- 
stance is  more  explosive  than  mercury  fulminate.  It  explodes  even 
when  shaken  under  the  mother  liquor.  When  dry  it  has  to  be  handled 
with  the  greatest  care  as  it  explodes  even  when  mixed  carefully  with 
copper  oxide.  (ClHg).  When  treated  with  alkalies  it  gives  aldehyde 
resin. 

Mercuri-nitritemercuri-acetaldehyde.5 

This  substance  is  obtained  from  the  action  of  acetylene  on  a  solu- 

iLasserre,  J.  pharm.  c7iiw.,(6)   22   (1905),  246.     Vhem.  Zentr.  1905  II  1125. 
.,•      2Auld   and    Hantzsch,   Ber.   38    (1905),   2684.      Hofmann,   Ber.    31    (1898),    1904; 
33  (1900),  1331. 

8Nef,  Ann.  298  (1897),  316. 

4  Hofmann,  Ber.  38  (1905),  2000. 

•Ibid.  2004. 

154 


DERIVED  FROM  ALDEHYDES  AND  KETONES       155 

tion  of  mercuric  nitrate  containing  an  excess  of  potassium  nitrite.  It 
forms  a  bright  yellow  powder.  (CHNHg) . 

Miscellaneous  reactions  of  acetaldehyde. 

Acetaldehyde  reacts  with  an  acid  solution  of  mercuric  sulfate  giv- 
ing a  product  which  is  formulated  as  CH3  —  CH0.2HgO.HgS04. 6 
(CHHg,S04). 

Acetaldehyde  reacts  with  a  slightly  alkaline  solution  of  mercuric 
oxide  in  sodium  sulfite  giving  a  substance  which  is  believed  to  be 

0 

/    \ 

Hg  =  CH  —  CH  Hg.  7      (CHHg) .    Dilute  nitric  acid  and  po- 

\    / 
0 

tassium  cyanide  decompose  it  giving  acetaldehyde.  Apparently  hydro- 
chloric acid  does  not  decompose  it  as  a  solution  of  the  substance  in 
hydrochloric  acid  gives  no  action  with  sodium  hydroxide  or  potassium 
iodide.  Sulfides  give  mercuric  sulfide.  Higher  aldehydes  react  with 
the  alkaline  sodium  sulfite  solution  of  mercuric  oxide  giving  mercury 
compounds.8 

Alcohol  treated  with  mercuric  nitrate  gives  a  white  precipitate 
which  is  probably  a  tri-mercurated  acetaldehyde.9 

Mercury  Compounds  of  Ketones. 

Acetone  reacts  with  mercury  compounds  giving  a  variety  of  sub- 
stances to  which  many  different  formulas  have  been  assigned.  Many, 
of  these  substances  are  written  as  double  compounds  of  acetone  with 
mercuric  oxide  or  basic  mercuric  salts. 

2Me2C0.3HgO,10  4Me2CO.6HgS04.9HgO  and  Me.CO^HgSC^.SHgO,11 
Me2C0.2HgO,12  3Me2C0.5HgS04.5HgO  and  Me2C0.2HgS04.3Hg0.13 
5Me2C0.8HgS04.12Hg0.14 

"Deniges,  Ann.  chim.  phys.   (7)  18   (1899),  396. 
'Leys,  Bull.  soc.  chim.   (3)   33   (1905),  1318. 
8  Leys,  loc.  cit. 

"Biilmann,  Ber.  35  (1902),  2588.  Compare  Gerhardt,  Ann.  80  (1851),  111; 
Cowper,  J.  Chem.  Soc.  39  (1881),  242;  Hofmann,  Ber.  31  (1898),  2783. 

10  Reynolds,   Chem.  News  23    (1871),   217.     Z.   Chem.    (2)    7    (1871),   254.     Ber.  4 
(1871),  483. 

11  Oppenfeeimer,  Ber.  32   (1899),  986.     Hofmann,  Ber.  31    (1898),  399. 
"Lasserre,  J.  pharm.  chim.   (6)   22   (1905),  246.     Chem.  Zentr.  1905  II  812,  1125. 
"Biilmann,  Ber.  35   (1902),  2584.  Hofmann,  loc.  cit. 

"Deniges,  Ann.  chim.  phys.   (8)   12   (1907),  401. 


156  COMPOUNDS  OF  MERCURY 

An  extremely  complex  compound  with  ammonium  chloride,  mercuric 
chloride,  and  hydroxylammonium  chloride  has  been  reported.15  It  is  as- 
signed the  formula  2Me2C0.5HgCl2.2NH4C1.2(NH2OH.HCl). 

Another  series  of  compounds  of  acetone  is  known.  These  are  form- 
ulated as  derivatives  of  an  ether-like  molecule  formed  by  the  elimina- 
tion of  water  from  two  molecules  of  an  acetone  hydrate.  This  hypo- 
thetical substance  would  have  the  formula 

CH3  —  C  (OH)  —  O  —  C  (OH)  —  CH3 

CH3  CH3 

and  could  be  called  "diacetone  hydrate." 

Tetra-acetoxymercuri  diacetone  hydrate, 

(AcOHg)  2CH  —  C  (OH)  —  0  —  C  (OH)  —  CH  (HgOAc)  2. 15a 

CH3  CH3 

Dry  mercuric  acetate  is  heated  with  acetone  at  100°  for  two  hours. 
The  mixture  is  filtered  and  the  filtrate  is  evaporated  to  a  yellow  oil. 
This  is  dissolved  in  a  little  alcohol  and  allowed  to  stand.  White  flakes 
slowly  separate.  These  are  recrystallized  from  hot  alcohol  containing 
a  little  acetic  acid.  (CHHg).  M.P.  157°.  20  per  cent  hydrochloric 
acid  and  potassium  cyanide  solution  decompose  the  substance  liberat- 
ing acetone.  Potassium  hydroxide  gives  the  corresponding  hydroxy- 
mercuri  compound.  When  this  is  dried  in  a  vacuum  it  becomes  the 
anhydro  compound, 

Hg  Hg 

/      \  /      \ 

0  CH  — C(OH)— O  — C(OH)— CH  0.     (CHHg). 

\      /  I  .1  \      / 

Hg  CH3  CH3  Hg 

It  is  insoluble  in  water  and  common  solvents.  It  is  easily  soluble  in 
dilute  hydrochloric  acid  and  potassium  cyanide  solution  with  the 
formation  of  acetone.  The  acetate  reacts  with  ammonium  oxalate 
giving  a  corresponding  complex  oxalate.  (CHHg).  A  water  solution 
of  the  acetate  reacts  with  sodium  chloride  solution  giving  a  precipitate 
of  the  corresponding  chloride.  (CHHg).  The  chloride  is  insoluble  in 
water  and  common  solvents. 

18  Grigorowitsch,  Chem.  Zentr.  1906  I  743. 
1Ba  Sand  and  Genssler,  Ber.  36   (1903),  3704. 


DERIVED  FROM  ALDEHYDES  AND  KETONES        157 

Tri-mercuri  diacetone  hydrate, 

HO  — Hg  — CH Hg  — CH  — Hg  — OH 

CH3  —  C  (OH)  —  0  —  C  (OH)  —  CH3.  16 

Acetone  is  treated  with  freshly  precipitated  mercuric  oxide  and  ba- 
rium hydroxide  solution.  A  syrup  is  obtained  which  is  soluble  in 
water.  (CHHg).  It  is  indifferent  to  phenyl  hydrazine  and  hydroxyl- 
amine.  When  the  water  soluble  oil  stands  in  contact  with  bases  it 
changes  to  an  insoluble  polymer.  (CHHg) .  Treatment  of  the  oil  with 
dilute  hydrochloric  acid  gives  mercuric  chloride  and  acetone  at 
once.  Bromine  gives  dibromacetone  which  can  be  removed  by 
steam  distillation  and  changed  by  hydroxylamine  to  methyl  glyoxime, 
CH3  —  C  =  NOH.  The  oil  forms  a  well  crystallized  picrate.  (Hg, 


H20,  picric  acid) .  Long  boiling  of  either  the  soluble  or  insoluble  form 
of  the  hydroxide  with  alkalies  gives  acetone  and  acetone  mercarbide, 

Hg  — 0 

/        / 

CH3  — CO  — C  — Hg  ,     (CHHg). 

\ 
Hg  — OH 

The  corresponding  chloride, 

ClHg  — CH Hg  — CH  — HgCl, 

CH3  —  C  (OH)  —  0  —  C  (OH)  —  CH3 

is  made  from  the  hydroxide  by  careful  addition  of  dilute  hydrochloric 
acid.  It  is  difficultly  soluble  in  alcohol  but  easily  soluble  in  pyridine 
and  aniline.  (ClHg).  It  turns  yellow  and  melts  at  110°.  It  forms  an 
amorphous  platinichloride  which  decomposes  at  178°.  (Pt).  The  bro- 
mide is  made  like  the  chloride  and  has  similar  properties.  It  forms 
small  white  needles  melting  at  127°.  (BrHg) .  The  iodide  is  made  from 
the  base  by  adding  potassium  iodide  and  cold  dilute  acetic  acid.  It 
is  more  soluble  in  alcohol  and  ether  than  the  other  halides.  M.P.  104°. 
(IHg). 

Acetone  treated  with  yellow  mercuric  oxide  and  sodium  hydroxide 
solution  at  room  temperature  for  a  long  time  gives  a  white  com- 

18Auld  and  Hantzsch,  Ber.  33  (1905),  2678. 


158  COMPOUNDS  OF  MERCURY 

pound  which  reacts  with  dilute  nitric  acid  forming  a  mercarbide, 
C3Hg3H50(N03)2.  This  substance  can  also  be  made  from  acetone  and 
an  acid  mercuric  nitrate  solution.  When  the  nitrate  is  treated  with 
sodium  hydroxide  it  gives  an  explosive  compound,  C3Hg3H703.  17 

Acetone  reacts  with  alkaline  mercuric  cyanide  solution  giving 
an  insoluble  white  powder,  C5Hg3H2ON2.  (CHNHg).  Dilute  hydro- 
chloric acid  removes  all  of  the  mercury.  It  probably  has  the  structure, 
CN  — Hg  — CH  — CO  — CH  — Hg  — CN.  18 


Hg 

Acetone  reduced  in  acid  solution  at  a  mercury  cathode  forms  mer- 
cury di-isopropyl.19 

Monochloracetone  reacts  with  acid  mercuric  sulfate  solution  giving 
a  compound  which  is  formulated  as  C1CH2  —  CO  —  CH3.2HgS04. 
3HgO.  (ClHg,S04).  It  decomposes  explosively  at  1330/ 


M 


Mercury  Derivatives  of  Higher  Ketones. 

Methylethyl  ketone  reacts  with  an  acid  mercuric  sulfate  solution 
forming  a  precipitate,  4MeEtC0.6HgS04.9Hg0.21  Methyl  ethyl  ke- 
tone also  reacts  with  mercuric  acetate  much  as  acetone  does  giving  a 
tetra-acetoxymercuri  derivative  of  the  diketone  hydrate.  This  sub- 
stance forms  "an  oxonium  picrate"  with  one  half  molecule  of  picric 
acid.  (CHNHg). 

Higher  ketones  such  as  diethyl  ketone,  dipropyl  ketone,  and  di- 
butyl  ketone  give  mercury  compounds  of  doubtful  constitution.22 

Acetyl  acetone  gives  a  mixture  of  mercury  compounds.23 

Mesityl  oxide  and  phorone  give  mercury  compounds  which  have  not 
been  studied.24 

Allyl  acetoxime  reacts  with  mercuric  acetate  giving  a  compound 
which  forms  an  iodide  of  the  formula, 

"Hofmann,  Ber.  31   (1898),  1908,  2213. 

"Marsh  and  Fleming-Struthers,  Proc.   Chem.  Soc.  21    (1905),  248.     Chem.  Zentr. 
1906  I  229.     J.  Chem.  Soc.  87   (1905),  1878;  95    (1909),  1778. 
'"Tafel,  Bcr.  39   (1906),  3626. 
20Deniges,  Ann.  chim.  phys.  (7)  18   (1899),  400. 

21  Deniges,  loc.  cit. 

22  Marsh   and  Fleming-Struthers,  loc.   cit.     Denig&s,   loc.   cit.     Auld  and   Hantzsch, 
loc.  cit.     Leys,  Bull.  soc.  chim.  (3)  33  (1905),  1320.     Reynolds,  Chem.  News  23  (1871), 
217.     Z.  Chem.  (2)  7  (1871),  254. 

2SBiilmann,  Ber.  35   (1902),  2585. 

2*  Hofmann  and  Sand,  Ber.  33   (1900),  1340.  , 


DERIVED  FROM  ACID  AMIDES  159 

CH3  —  C  =  N  —  0  —  CH  —  CH2  —  Hgl.25 
CH2 CH2 

Mercury  Compounds  of  Amino  Acids. 

Mercuric  acetate  and  other  mercuric  salts  are  much  used  in  pre- 
cipitating amino  acids.  The  compounds  obtained  have  the  mercury 
attached  to  N,  to  0,  or  to  both  and  are  therefore  not  true  organic  mer- 
cury compounds. 

Mercury  Derivatives  of  Cyano  Acids. 

Hydroxymercuricyanoacetic  acid.26 

Mercuric  oxide  is  shaken  with  slightly  more  than  one  molecule  of 
cyanoacetic  acid.  Reaction  starts  at  once  and  in  two  days  all  of  the 
oxide  is  gone  and  a  white  crystalline  precipitate  is  left.  (CHNHg) .  It 
is  soluble  in  alkalies.  Ammonium  cyanoacetate  gives  a  more  com- 
plicated mercury  compound.  Sodium  cyanoacetate  reacts  with  mer- 
curic oxide,  giving  the  sodium  salt  of  hydroxymercuricyanoacetic  acid. 
(NNaHg) .  The  potassium  and  barium  salts  have  been  made  and  an- 
alyzed. 

Hydroxymercuricyanoacetic  ethyl  ester. 

Ethyl  cyanoacetate  is  treated  with  mercuric  acetate  in  methyl  al- 
cohol. A  white  crystalline  precipitate  of  the  hydroxide  separates. 
This  is  filtered  at  once  and  washed.  (CNHg).  The  methyl  ester  is 
prepared  in  the  same  way.  (NHg) . 

a-Hydroxymercuri-a-cyanopropwnic  acid. 

It  is  a  yellowish  white  precipitate  prepared  from  the  acid  and  mer- 
curic oxide.  (CHNHg).  It  is  soluble  in  alkalies. 

Mercury  Derivatives  of  the  Acid  Amides. 

Acid  amides  readily  dissolve  mercuric  oxide  forming  N  —  Hg  com- 
pounds of  the  general  formula  (R  —  CO  —  NH  — )  2Hg,  which  are  usu- 
ally water  soluble.  The  N  —  Hg  linkage  is  easily  split  by  dilute  acids, 
sulfides,  and  iodides,  but  usually  not  by  bases.27  It  is  often  said  that 

25  Sand,  Ann.  329  (1903),  181. 

26  Petterson,  J.  prakt.  Chem.   (2)   86  (1912),  458. 

"Ley  and  Schaefer,  Ber.  35  (1902),  1309.  B.  Fischer  and  Grutzner,  Arch.  Pharm. 
232  (1894; ,  329.  Chem.  Zentr.  1894  II  738.  Dessaignes,  Ann.  82  (1852),  231. 


160  COMPOUNDS  OF  MERCURY 

the  linkings  C  —  Hg  and  N  —  Hg  differ  entirely  in  their  stability 
toward  various  reagents.  This  statement  is  true  only  in  the  most 
general  way.  There  are  many  C  —  Hg  compounds  which  react  as 
rapidly  with  iodides  as  do  the  mercury  acid  amides.  The  mercurated 
phenols  for  example  react  with  potassium  iodide  giving  phenol,  po- 
tassium hydroxide,  and  mercuric  iodide  in  the  same  way  that  mercury 
acetamide  will  give  acetamide,  potassium  hydroxide,  and  mercuric 
iodide.28 

Mercury  formamide  exists  only  in  solution.29 

A  solution  of  mercuric  oxide  in  the  least  possible  amount  of  forma- 
mide poured  into  a  large  amount  of  alcohol  gives  a  white  amorphous 
precipitate  of  N-hydroxymercuriformamide,  H  —  CO : —  NH  —  HgOH. 
When  this  is  dissolved  in  hydrochloric  acid  it  gives  compounds, 
2HCONH-HgC1.3HCl  and  HCONH  -  HgCl.HCl. 

Mercury  acetamide,  (CH3CONH  — )  2Hg. 30 

Yellow  mercuric  oxide  is  added  to  melted  acetamide  in  a  porcelain 
dish.  The  temperature  is  slowly  raised  to  180°.  All  the  oxide  dis- 
solves giving  a  slightly  yellow  solution.  The  melt  is  cooled  and  dis- 
solved in  water,  filtered,  and  evaporated  to  dry  ness  on  the  water  bath. 
The  product  is  recrystallized  from  methyl  alcohol.  Yield  80  per  cent. 
M.P.  195°. 

The  preparations  and  properties  of  the  other  mercury  acid  amides 
are  so  similar  to  those  of  mercury  acetamide  that  they  will  simply,  be 
listed  with  their  references. 
Mercury  monochloroacetamide.31 

Mercury  cyanoacetamide.     The  compound  formed  from  cyanoaceta- 
mide  may  have  the  mercury  attached  to  carbon  instead  of  to  nitro- 
gen.318 
Mercury  nitroacetamide.32 

28Whitmore  and  Middleton,  J.  Am.  Chem.  Soc.  43   (1921),  622. 

28  Fischer  and  Griitzner,  loc.  cit. 

30Strecker,  Ann.  103  (1857),  324.  W.  Morkownikoff,  Z.  Chem.  (1)  6  (1863),  535. 
Oppenheim  and  Pfaff,  Ber.  1  (1874),  624.  Andre",  Compt.  rend.  102  (1886),  116.  Ley 
and  Kissel,  Ber.  32  (1899),  1359.  Schoeller  and  Schrauth,  Ber.  42  (1909),  784. 
Franklin,  Am.  Chem.  J.  47  (1912),  393. 

31  Menschutkin  and  Jermolajeff,  Z.  Ch&m.  (2)  7  (1871),  5.  Francesconi  and 
de  Plato,  Gazz.  chim.  ital.  33  I  (1903),  228.  Chem.  Zentr.  1903  II  24. 

81*  Ley  and  Schaefer,  loc.  cit. 

"Prager,  Monatsh.  33  (1912),  1289. 


DERIVED  FROM  ACID  AMIDES  161 

Mercury  propionamide.83 

Mercury  butyramide.34 

Mercury  oxamide.35 

Mercury  succinamide.36 

Mercury  phenyl  succinamide.36a 

Mercury  succinimide.37  Conductivity  measurements  indicate  that  the 
linkage  Hg  —  N  =  of  the  mercury  imides  is  more  stable  than 
the  linkage  Hg  —  NH  —  of  the  corresponding  amides. 

Mercury  tartramide.38 

Mercury  fumaramide.39 

Mercury  urea  compounds.40 

Mercury  compounds  of  diethyl  barbituric  acid.41 

Mercury  compounds  of  violuric  acid.42 

Mercury  Derivatives  of  Dithiocarbamine  Compounds. 

The  treatment  of  various  amino  compounds  with  carbon  disulfide 
gives  di-thiocarbamine  derivatives  from  which  S  —  Hg  compounds  are 
easily  prepared.  A  typical  example  of  this  reaction  is  shown  by  the 
reaction  of  methylaminoacetic  ethyl  ester  with  carbon  disulfide  and 
ether  giving  a  complex  compound  which  reacts  with  mercuric  chloride 
forming  a  mercury  compound  which  on  saponification  gives  the  sub- 
stance Hg(— S  — CS  — N(CH3)  — CH2  — C02Na)2.43 

Other  N  —  Hg  Compounds. 

Camphorimide  forms  a  mercury  compound  with  properties  resembling 
those  of  mercury  succinimide.44 

83  Ley  and  Fischer,  Z.  anorg.  Chem.  82  (1913),  336.  Sestinl,  Z.  Chem.  (2)  7 
(1871),  35. 

"Dessaignes,  loc.  cit.  234.     Ley  and  Schaefer,  Ber.  35   (1902),  1312. 

"Ley  and  Schaefer,  loc.  cit.  Schutz,  Marsh,  and  Geuther,  Z.  Chem.  (2)  4 
(1868),  303. 

3«Ley  and  Kissel,  loc.  cit.     Menschutkin,  Ann.  162   (1872),  171. 

S8a  Menschutkin,  loc.  cit. 

87  Ley  and  Schaefer,  loc.  cit.  Menschutkin,  loc.  cit.  Landsberg,  Ann.  215  (1882), 
209.  Dessaignes,  loc.  cit. 

"Grote,  Ann.  130   (1864),  203. 

39  Dessaignes,  loc.  cit. 

40  Dessaignes,    loc.    cit.      Novak,    Chem.    Zentr.    1873    154.      Pfliiger,    Chem.   Zentr. 
1888  559.     Pesci,  Z.  anorg.  Chem.  15    (1897),  231.     Ley  and  Schaefer,  loc.  cit.     Neu- 
berg  and  Kerb,  Biochem.  Z.  40  (1912),  506. 

"Lami,   Chem.  AT>st.  10    (1916),  2613. 

^Auld,  J.  Chem.  Soc.  91   (1907),  1046. 

*•  Poulenc  Freres,  D.  R.  P.  235,  356.     Chem,  Zentr.  1911  II  170. 

44  Ley  and  Schaefer,  loc.  cit. 


162  COMPOUNDS  OF  MERCURY 

Uric  acid  forms  a  variety  of  mercury  compounds.45 

Theobromine  and  theophylline  heated  with  mercuric  acetate  or  mer- 
curic oxide  give  mercury  compounds  which  are  stable  to  ammonium 
sulfide  indicating  that  they  are  C  —  Hg  compounds.46 

Mercuric  cyanide.  Opinions  differ  as  to  whether  mercuric  cyanide  is 
a  C  —  Hg  or  an  N  —  Hg  compound.47 

Its  very  slight  activity  with  acids  would  indicate  the  C  —  Hg 
linkage.  The  fact  that  it  is  practically  as  transparent  to  light  as  pure 
water  also  indicates  the  C  linkage  as  a  high  degree  of  transparency  is 
associated  with  it  more  than  with  the  N  —  Hg  linking.48 

Mercury  Derivatives  of  Diazoacetic  Esters. 

Mercury  bis-diazoacetic  ethyl  ester,          N  =  N 

\   / 
Hg(-C  — C02Et)2.49 

The  calculated  amount  of  mercuric  oxide  is  dissolved  in  diazoacetic 
ethyl  ester.  The  product  is  extracted  with  ether  in  which  the  mercury 
compound  is  readily  soluble.  (CHNHg).  M.P.  104°.  It  explodes  on 
concussion.  It  is  volatile  with  steam  with  partial  decomposition.  The 
methyl  ester  is  prepared  in  a  similar  way.  It  is  less  soluble  in  ether 
than  the  ethyl  ester.  (N).  M.P.  123°,  with  slight  decomposition. 
Treated  with  hydrogen  sulfide  it  gives  mercuric  sulfide  and  a  compound 
containing  11.8  per  cent  nitrogen  whereas  diazoacetic  ester  contains 
24.6  per  cent.  This  compound  has  not  been  identified. 

Mercury  diazoacetic  ester  reacts  with  water  giving  metallic  mer- 
cury, nitrogen,  and  a  clear  solution  containing  alcohol,  oxalic  acid,  and 
glycollic  acid. 

48  Gmelin-Kraut-Friedheim-Peters,   Handbuch,  V-II    455. 

49  Fraenkel,  Arznelrmttelsynthese,  4th  Ed.  1919,  676. 

47  Kieseritzky,   Z.   physik.    Chem.   28    (1899),    406.      Ley   and    Schaefer,   Z.   physik. 
Chem.  42   (1903),  704>. 

48  Ley  and  Fischer,  Z.  anorg.  Chem.  82   (1913),  337. 

"Curtius  and  Buchner,  J.  prakt.  Chem.  (2)  38  (1888),  411.  Buchner.  Ber.  28 
U895),  2J6, 


Chapter  IX. 

Mercury  Derivatives  of  Aromatic  Hydrocarbons  and 
Mtro  Compounds. 

Mercury  Phenyl  Compounds. 

Mercury  Diphenyl. 
Preparation. 

1.  From  bromobenzene  and  sodium  amalgam.1 

Equal  volumes  of  120-140°  xylene  and  bromobenzene  are  mixed 
with  one-tenth  volume  of  ethyl  acetate  and  heated  with  an  excess  of 
2.7  per  cent  sodium  amalgam  in  an  oil  bath  at  110°  and  then  at  about 
130°  for  eight  hours.  The  mixture  is  filtered  hot  and  then  repeatedly 
extracted  with  hot  benzene.  All  the  solutions  are  combined  and  evapo- 
rated on  the  steam  bath  and  then  on  the  oil  bath  up  to  160°.  It  is 
best  to  carry  out  the  latter  part  of  the  distillation  under  diminished 
pressure.  The  residue  is  poured  out  and  allowed  to  cool.  The  crystals 
which  form  are  washed  with  cold  alcohol  as  long  as  any  color  is  re- 
moved. The  residue  is  almost  pure  white.  The  yield  with  1  per  cent 
amalgam  is  given  as  27  per  cent  and  that  with  2.7  per  cent  amalgam 
as  46  per  cent.  The  better  yield  with  the  more  concentrated  amalgam 
is  in  sharp  contrast  to  the  results  with  aliphatic  halides. 

Some  mercury  diphenyl  is  obtained  as  a  by-product  in  the  action 
of  phenyl  bromide,  ethyl  chloroformate,  and  sodium  amalgam  form- 
ing ethyl  benzoate.2  It  has  been  suggested  that  the  mercury  diphenyl 
is  an  intermediate  product  in  the  formation  of  the  ester.  Apparently 
the  action  of  ethyl  chloroformate  and  mercury  diphenyl  has  not  been 
studied. 

2.  From  bromobenzene,  mercuric  chloride,  and  sodium.3 

This  reaction  carried  out  in  benzene  gives  mercury  diphenyl.     It 

iDreher  and  Otto,   Ber.  2    (1869),   542.     Ann.  154    (1870),  94.     Ladenberg,  Ann. 
173  (1874),  151.     Michaelis,  Ann.  181   (1876),  290.     Aronheim,  Ann.  194   (1878),  148. 
'Wurtz,  Compt.  rend.  68  (1869),  1300.     Ann.  Spl.  1  (1870),  125. 
8  Michaelis  and  Reese,  Ber.  15   (1882),  2877. 

163 


164  COMPOUNDS  OF  MERCURY 

seems  possible  that  this  reaction  could  be  developed  as  the  best  way 
for  making  mercury  diphenyl  as  the  difficulty  of  bringing  the  bromo- 
benzene  in  contact  with  the  amalgam  might  be  overcome  in  this  way. 

3.  From  phenyl  arsenious  oxide  and  mercuric  chloride.4 

A  solution  of  C6H5  —  AsO  in  sodium  hydroxide  is  heated  with  mer- 
curic chloride  forming  mercury  diphenyl. 

4.  From  phenyl  magnesium  bromide  and  mercuric  chloride.5 

The  Grignard  reagent  from  25  gm.  of  bromobenzene  boiled  with 
the  calculated  amount  of  mercuric  chloride  in  ether  for  1  hour  gives 
7.5  gm.  of  mercury  diphenyl. 

5.  From  phenyl  hydrazine  and  mercury  compounds.6 

10  gm.  of  phenyl  hydrazine  heated  with  mercuric  oxide  gives  4  gm. 
of  mercury  diphenyl.  Mercury  acetamide  acts  the  same  as  mercuric 
oxide. 

6.  From  phenyl  mercuric  iodide  and  sodium  amalgam.7 

The  reaction  is  carried  out  in  alcohol  or  better  in  dry  benzene. 

7.  From  phenyl  mercuric  acetate  and  sodium  stannite.8 

Phenyl  mercuric  acetate,  precipitated  in  finely  divided  form  by 
pouring  an  alcoholic  solution  into  water,  is  treated  with  an  alkaline 
sodium  stannite  solution.  A  black  solid  consisting  of  mercury  and 
mercury  diphenyl  is  formed.  The  latter  is  extracted  by  hot  benzene. 

8.  From   di- (phenylmercuri)    ammonium   acetate   and   sulfur   com- 
pounds.9 

The  compound,  (C6H5Hg)2NH2OAc,  obtained  from  phenyl  mer- 
curic acetate  and  ammonium  hydroxide,  is  heated  in  alcohol  with  car- 
bon disulfide,  thiocarbanilide,  or  various  thioureas.  Mercury  diphenyl 
is  one  of  the  products. 

9.  From  phenyl  mercuric  bromide  and  potassium  sulfide.10 

Long  boiling  of  the  substances  in  alcohol  gives  mercuric  sulfide, 
potassium  bromide,  and  mercury  diphenyl. 

«  D.  R.  P.  272,  289.  Chem.  Zentr.  1914  I  1469.  Fraenkel,  Arzneimittelsynthese, 
4th  Ed.  1919,  661. 

'Pfeiffer  and  Truskier,  Ber.  37    (1904),  1127. 

•Fischer  and  Ehrhard,  Ann.  199  (1879),  332.  Foster,  J.  Chem.  Soc.  73  (1898), 
791.  Foster,  Chem.  News  78  (1898),  250. 

7  Dreher  and  Otto,  loc.  cit.  115. 

•Dimroth,  Ber.  35   (1902),  2853. 

•Pesci,  Qtazz.  chim.  ital.  39  I  (1909),  150. 

*>  Dreher  and  Otto,  loc.  cit. 


DERIVED  FROM  AROMATIC  HYDROCARBONS        165 

Properties.^ 

Mercury  diphenyl  forms  small  white  glassy  needles.  M.P.  120° 
(121.80,12  125-6°  13).  It  is  best  recrystallized  from  hot  benzene  or 
chloroform.  (CHHg).  The  white  crystals  turn  yellow  in  light.  It  is 
insoluble  in  water,  easily  soluble  in  chloroform,  carbon  disulfide,  ben- 
zene, less  soluble  in  ether  and  boiling  alcohol.  It  is  slightly  volatile 
with  steam.  It  sublimes  on  heating  above  its  melting  point.  It  can- 
not be  distilled  under  ordinary  pressure  as  it  decomposes  giving  mer- 
cury, benzene,  diphenyl,  carbon,  and  other  products.  B.P.  10.5  204°. 
Its  density  varies  from  2.29  to  2.34. 

A  solution  of  mercury  diphenyl  in  chloroform  shows  no  absorption 
bands  as  it  is  remarkably  transparent  to  all  wave  lengths.  It  absorbs 
light  less  than  does  mercuric  iodide  whereas  benzene  absorbs  light 
more  than  hydrogen  iodide.14  It  absorbs  the  longer  wave  lengths  more 
than  does  benzene. 

Mercury  diphenyl  is  toxic.  It  has  a  very  irritating  effect  on  the 
eyes.15 

Reactions. 

1.  With  halogens. 

Dry  chlorine  gives  a  vigorous  reaction  forming  phenyl  mercuric 
chloride,  phenyl  chloride,  and  some  mercuric  chloride.16 

Iodine  in  alcohol  or  carbon  disulfide  gives  phenyl  mercuric  iodide 
and  phenyl  iodide.  An  excess  of  iodine  changes  the  former  to  mer- 
curic iodide. 

Thiocyanogen,  (SCN)2,  acts  like  a  halogen  giving  phenyl  thio- 
cyanate  and  phenyl  mercuric  thiocyanate.17 

2.  With  metals. 

Sodium  amalgam  and  alcohol  or  benzene  give  no  change. 

Lithium,  sodium,  and  potassium  react  vigorously  with  mercury  di- 
phenyl either  with  or  without  solvents.  Gray  insoluble  products  are 
obtained.18  This  result  is  somewhat  different  from  earlier  work  in 

"Dreher  and  Otto,  loc.  cit.  Wurtz,  loc.  cit.  Schroeder,  Ber.  12  (1879),  564. 
Krafft  and  Lyons,  Ber.  27  (1894),  1768.  Purvis  and  McClelland,  J.  Chem.  Soc.  101 
(1912),  1519.  Ley  and  Fischer,  Z.  anorg.  Chem.  82  (1913),  338. 

12  Chem.  Zentr.  1912  II  822. 

"Foster,  J.  Chem.  Soc.  73   (1898),  783. 

14  Ley  and  Fischer,  loc.  cit. 

1BLadenberg,  Ann.  173  (1874),  151. 

18  Dreher  and  Otto,  loc.  cit. 

1T  Soderback,  Ann.  419   (1919),  266. 

18Hilpert  and  Gruttner,  Ber.  46   (1913),  1679. 


166  COMPOUNDS  OF  MERCURY 

which  sodium  reacted  on  mercury  diphenyl  in  benzene  or  ligroin  so- 
lution forming  a  light  brown  precipitate  of  sodium  phenyl.19 

Magnesium  gives  magnesium  diphenyl.20 

Distillation  with  zinc  gives  zinc  diphenyl.  This  reaction  is  better 
carried  out  by  gently  heating  the  substances  for  two  minutes  in  an 
atmosphere  of  hydrogen  as  zinc  diphenyl  is  very  sensitive  to  oxygen 
and  moisture.21 

Heating  mercury  diphenyl  with  a  large  excess  of  cadmium  gives 
cadmium  diphenyl  but  the  reaction  does  not  run  to  completion.  The 
best  product  obtained  contains  only  76  per  cent  of  the  cadmium  com- 
pound. 

Mercury  diphenyl  heated  with  aluminum  in  a  stream  of  hydrogen 
or  nitrogen  gives  a  vigorous  reaction  when  the  temperature  reaches 
140°.  The  reaction  then  proceeds  spontaneously  with  the  formation 
of  aluminum  triphenyl.  Only  small  quantities  should  be  treated  at 
a  time  to  avoid  the  decomposition  of  the  aluminum  triphenyl  by  the 
strongly  exothermic  reaction.22 

Mercury  diphenyl  and  bismuth  on  heating  give  a  mixture  contain- 
ing 41  per  cent  of  bismuth  triphenyl. 

Mercury  diphenyl  heated  to  200°  with  zirconium  gives  no  action.23 
No  action  is  obtained  with  lead  or  tin.    Distillation  of  mercury  di- 
phenyl with  freshly  reduced  iron  or  copper  gives  considerable  diphenyl 
but  no  metallo-organic  compounds. 
3.     With  halides  of  non-metals. 

Boron  trichloride  heated  with  mercury  diphenyl  several  hours  at 
200°  gives  mercuric  chloride  and  phenyl  boron  dichloride.24  If  this 
substance  is  heated  with  mercury  diphenyl  for  24  hours  at  300°  it 
gives  diphenyl  boron  chloride  and  phenyl  mercuric  chloride. 

Silicon  tetrachloride  at  300°  forms  phenyl  mercuric  chloride  and 
phenyl  silicon  trichloride.25 

Stannic  chloride  and  mercury  diphenyl  react  without  heating.  The 
reaction  is  exothermic.  The  reaction  is  best  carried  out  in  80-100° 
ligroin  with  a  short  refluxing  under  a  condenser  protected  by  a  drying 

19Acree,  Am.  Chem.  J.  29   (1903),  588. 

2°Hilpert  and  Gruttner,  loc.  cit.     Fleck,  Ann.  276   (1893),  138. 

21  Dreher  and  Otto,  loc.  cit.     Hilpert  and  Griittner,  loc.  cit. 

22Hilpert  and   Gruttner,  Ber.   45    (1912),  2829. 

23  W.  Peters,  Ber.  41  (1908),  3173. 

2«Michaelis  and  Becker,  Ber.  13   (1880),  59;  15    (1882),  180. 

2eLadenberg,  Ann.  173    (1874),  152. 


DERIVED  FROM  AROMATIC  HYDROCARBONS        167 

tube.  The  products  are  phenyl  mercuric  chloride  and  diphenyl  tin 
dichloride.26 

Phosphorus  trichloride  heated  with  mercury  diphenyl  for  a  few 
hours  at  180°  gives  phenyl  mercuric  chloride  and  phosphenyl  chlo- 
ride, C6H5  —  PC12. 27 

Arsenic  trichloride  acts  more  rapidly  than  phosphorus  trichloride. 
At  250°  it  gives  phenyl  dichlorarsine  and  mercuric  chloride.  Phenyl 
mercuric  chloride  also  reacts  with  arsenic  trichloride.28  Phenyl  di- 
chlorarsine reacts  with  mercury  diphenyl  giving  a  small  amount  of 
triphenyl  arsine  and  considerable  diphenyl  chlorarsine.29 

Mercury  diphenyl  heated  with  antimony  trichloride  gives  phenyl 
mercuric  chloride  and  the  pentavalent  antimony  derivatives, 
(C6H5)3SbCl2  and  (C6H5)2SbCl3. 30 

Tellurium  dichloride  heated  with  mercury  diphenyl  to  225°  forms 
phenyl  chloride  and  mercury  telluride.31 

4.  With  acid  chlorides. 

Thionyl  chloride  warmed -gently  with  mercury  diphenyl  gives  a 
vigorous  reaction  forming  the  theoretical  amount  of  phenyl  mercuric 
chloride.  Only  a  small  amount  of  an  oil  containing  sulfur  is  formed.32 

Benzene  sulfone  chloride  refluxed  with  mercury  diphenyl  in  ben- 
zene gives  no  action.  Heated  in  a  tube  at  160°  it  gives  a  small  amount 
of  phenyl  mercuric  chloride  and  sulfobenzide.  Less  than  one  gram  of 
the  latter  substance  is  obtained  from  20  gm.  of  mercury  diphenyl.  If 
no  solvent  is  used  the  reaction  is  very  violent  forming  metallic  mer- 
cury, benzene,  hydrochloric  acid,  and  diphenyl.33 

p-Toluene  sulfone  chloride  heated  with  mercury  diphenyl  for  15 
hours  at  120°  in  benzene  solution  gives  a  good  yield  of  p-tolyl  mer- 
curic chloride  and  a  small  amount  of  a  sulfone.34  This  reaction  has 
not  been  studied  further. 

5.  With  acids. 

Dry  hydrogen  chloride  gas  acts  on  mercury  diphenyl  with  evolution 

MAronheim,  Ann.  194  (1878),  148. 

27  Schwarze,  J.  prakt.  Chem.   (2)    10    (1874),   223.     Michaelis  and   Graeff,   Ber.  8 
(1875),  922.     Michaelis,  Ann.  181   (1876),  291. 

28  Michaelis  and  LaCoste,  Ann.  201  (1880),  196  ff. 
"    29  Michaelis  and  Link,  Ann.  207   (1881),  195. 

30  Michaelis  and  Reese,  Ber.  15  (1882),  2877.  Hasenbaumer,  Ber.  31  (1898), 
2911. 

"Krafft  and  Lyons,  Ber.  27   (1894),  1768. 
"Heumann  and  Kochlin,  Ber.  16   (1883),  1626. 
"Otto,  Ber.  18   (1885),  246. 
"/bid.  249. 


168  COMPOUNDS  OF  MERCURY 

of  heat  and  the  formation  of  benzene  and  mercuric  chloride.  Concen- 
trated hydrochloric  acid  gives  the  same  result  on  heating.  Fairly  con- 
centrated sulfuric  acid  gives  similar  results.  Concentrated  or  fuming 
nitric  acid  gives  mercuric  nitrate  and  nitrobenzene.  The  reaction  of 
nitric  acid  is  violent  even  when  the  reaction  is  carried  out  in  carbon 
disulfide  solution  at  -15°. 35 

A  solution  of  hypochlorous  acid  acts  like  free  chlorine  forming 
chlorobenzene  and  phenyl  mercuric  chloride. 

Boiling  glacial  acetic  gives  benzene  and  phenyl  mercuric  acetate. 
If  mercury  diphenyl  is  heated  with  glacial  acetic  acid  at  220°  the 
products  are  benzene,  diphenyl,  a  tar,  and  metallic  mercury.  No 
phenol  or  phenol  ester  is  obtained.  This  result  is  in  sharp  contrast 
to  the  action  of  mercury  dibenzyl  under  similar  conditions  forming 
benzyl  acetate.38  Formic,  propionic,  and  myristic  acids  give  benzene 
and  phenyl  mercuric  salts. 

6.  With  acid  anhydrides. 

Nitrogen  tetroxide  in  chloroform  solution  gives  phenyl  mercuric  ni- 
trate and  nitrosobenzene.  Nitric  oxide  gives  no  action  with  mercury 
diphenyl.  Nitrogen  trioxide  forms  phenyl  mercuric  nitrate  and  benzene 
diazonium  nitrate.37 

Chlorine  monoxide  gives  a  violent  reaction  with  mercury  diphenyl 
forming  carbon,  mercuric  chloride,  and  phenyl  mercuric  chloride.  No 
diphenyl  oxide  is  obtained.38 

Sulfur  trioxide  reacts  with  mercury  diphenyl  forming  mercuric 
benzenesulfonate.  Sulfur  dioxide  gives  no  reaction  in  benzene  solution. 
If  it  is  bubbled  through  melted  mercury  diphenyl  a  reaction  takes 
place.  The  product  is  not  a  sulfinate.39 

7.  With  mercuric  salts. 

Mercury  diphenyl  in  acetone  reacts  with  mercuric  chloride  in  the 
same  solvent  giving  an  immediate  precipitate  of  phenylmercuric  chlo- 
ride. Yield  94  per  cent.  A  similar  reaction  takes  place  in  alcohol 
solution.40  It  is  evidently  unnecessary  to  use  a  high  temperature  in 
this  reaction.41 

"Dreher  and  Otto,  Ann.  154   (1870),  97,  124. 

"•Dreber  and  Otto,  loc.  cit.  117.     Otto,  J.  prakt.  Chem.  (2)   1   (1870),  179.     L.  W. 
Jones,  J.  Am.  Chem.  Soc.  40   (1918),  1268. 
31  Bamberger,  Ber.  30  (1897),  509. 
88  Dreber  and  Otto,  loc.  cit. 
38  Otto,  J.  prakt.  Chem.  (2)   1   (1870),  185. 
«°Steinkopf,  Ann.  413   (1917),  313,  329. 
"Dreher  and  Otto,  Ann.  154  (1870),  113. 


DERIVED  FROM  AROMATIC  HYDROCARBONS        169 

Mercury  diphenyl  heated  with  mercurous  chloride  to  160°  in  alco- 
hol gives  phenyl  mercuric  chloride  and  metallic  mercury.42 

Mercuric  acetate  is  said  not  to  react  with  mercury  diphenyl  in 
alcohol  at  ordinary  temperature.  Heated  to  120°,  the  mixture  gives 
phenylmercuric  acetate.43  Mercury  diphenyl  heated  with  an  excess  of 
mercuric  acetate  to  150°  without  a  solvent  gives  a  mixture  of  1,  4-di- 
acetoxymercuribenzene,  1,  2,  4-tri-acetoxymercuribenzene,  and  1,  2,  4, 
5-tetra-acetoxymercuribenzene.44 

Mercuric  cyanide  heated  with  mercury  diphenyl  in  alcohol  at  120° 
gives  phenylmercuric  cyanide.  The  sulfocyanate  gives  a  similar  re- 
action. 

8.  With  organic  halides. 

Ethylene  dibromide  and  mercury  diphenyl  gives  no  action  when 
refluxed.  If  heated  in  a  tube  for  ten  hours  at  200°  they  give  phenyl- 
mercuric bromide.  No  other  products  of  the  reaction  have  been  identi- 
fied.45 

Mercury  diphenyl  heated  with  benzal  chloride  at  150°  gives  phenyl- 
mercuric chloride  and  triphenyl  methane.46  This  is  one  of  the  very 
rare  cases  in  which  a  compound  with  the  linkage  C  —  Hg  reacts  with 
one  with  the  linkage  X  —  C  giving  a  compound  having  a  new  C  —  C 
linkage. 

Heating  mercury  diphenyl  with  allyl  iodide  gives  diallyl,  phenyl- 
mercuric iodide,  and  diphenyl.47 

9.  With  oxidizing  agents. 

Mercury  diphenyl  does  not  absorb  oxygen  from  the  air.  Long 
boiling  with  benzene  and  silver  oxide  gives  no  change  except  for  the 
formation  of  a  minute  amount  of  metallic  silver. 

Heating  with  potassium  permanganate  solution  gives  manganese 
dioxide,  oxalic  acid,  and  phenylmercuric  hydroxide  which  can  be 
changed  to  phenylmercuric  chloride  by  hydrochloric  acid.48 

10.  With  sulfur. 

When  a  mixture  of  mercury  diphenyl  and  sulfur  is  heated  in  a  re- 
tort until  mercuric  sulfide  begins  to  form  the  reaction  continues  with- 

42  Otto,  loc.  cit. 

43  Otto,  loc.  cit.  179. 

*4Pesci,  Atti.  accad.  Lined  (5)  8  I   (1899),  130.     CJiem.  Zentr.  1899  I  734. 
45  Dreher  and  Otto,  loc.  cit.  128. 
48  Kekule"  ,and  Franchimont,  Ber.  5   (1872),  907. 
«Suida,  Monatsh.  1    (1880),  715. 

"Dreher  and  Otto,  loc.  cit.  Ber.  2  (1869),  544.  Otto,  J.  prakt.  Chem.  (2)  29 
(1884),  137. 


170  COMPOUNDS  OF  MERCURY 

out  further  heating.  The  principal  organic  product  is  diphenyl  sulfide. 
Some  thiophenol  is  formed.  Any  excess  of  sulfur  remains  unchanged. 
If  the  mercury  diphenyl  is  dissolved  in  alcohol  no  reaction  takes  place 
with  sulfur  below  140°.  At  that  temperature  mercuric  sulfide  and 
diphenyl  sulfide  are  formed.49 

11.  With  other  metallophenyl  compounds. 

The  various  equilibrium  systems  involving  the  phenyl  derivatives 
of  mercury,  bismuth,  antimony,  and  tin  have  been  studied.  No  evi- 
dence of  the  existence  of  molecular  complexes  is  found.50 

12.  With  aromatic  iodidechlorides. 

Mercury  diphenyl  mixed  with  phenyl  iodidechloride  and  water 
forms  diphenyl  iodonium  chloride,  (C6H5)2I  — Cl,  and  phenylmercuric 
chloride  or  mercuric  chloride  depending  on  the  amount  of  the  iodide- 
chloride  used.  Similar  results  are  obtained  with  the  iodidechlorides 
of  o-  and  p-tolyl  and  beta  naphthyl.51 

13.  With  N-halogen  acid  amides,52 

N-Bromoacetamide  heated  with  mercury  diphenyl  in  dry  benzene 
gives  phenyl  mercuric  bromide,  benzene,  and  methyl  isocyanate.  The 
latter  is  identified  by  its  action  with  aniline  forming  monophenyl  urea. 
The  reaction  will  also  take  place  at  room  temperature  if  the  mixture 
is  left  for  a  few  minutes  in  direct  sunlight.  In  this  reaction  the  mer- 
cury diphenyl  obviously  reacts  with  the  molecule  of  hydrobromic  acid 
which  is  easily  split  off  from  the  bromoamide. 

Similar  reactions  take  place  between  mercury  diphenyl  and  bromo- 
amides  of  the  following  acids,  benzoic,  o-,  m-,  and  p-nitrobenzoic  acids. 

N-Chloroacetanilide  is  incapable  of  losing  a  molecule  of  acid  and 
does  not  react  with  mercury  diphenyl  even  on  boiling  the  mixture  in 
dry  benzene  for  14  hours. 

Other  Phenyl  Mercuric  Compounds. 

Phenylmercuric  hydroxide. 

This  substance  is  obtained  by  refluxing  phenylmercuric  chloride 
and  moist  silver  oxide  in  alcohol.  The  filtrate  from  the  silver  chloride 
is  evaporated  leaving  small  white  rhombic  prisms.  The  hydroxide 

"Dreher   and   Otto,   loc.   cit. 

K>Cambi,  Atti.  accad.  Lincei  (5)   21  I   (1912),  773.     Chem.  Zentr.  1912  II  822. 

«  Willgerodt,  Ber.  31  (1898),  915. 

82Kharasch,  J.  Am.  Chem.  Soc.  43   (1921),  May    ? 


DERIVED  FROM  AROMATIC  HYDROCARBONS       171 

is  slightly  soluble  in  cold  water,  more  in  hot,  and  is  soluble  in  alcohol 
and  benzene.  In  purifying  the  compound  air  must  be  excluded  as  it 
absorbs  carbon  dioxide  readily.  When  heated  it  softens  at  160°  but 
does  not  melt  entirely  at  200°.  Apparently  a  new  compound  is 
formed  during  the  heating.  If  it  is  placed  in  a  bath  at  200°  without 
preliminary  heating  it  melts  but  immediately  solidifies  and  does  not 
melt  again.  The  hydroxide  is  a  strong  base  as  its  water  solution  is 
strongly  alkaline,  absorbs  carbon  dioxide,  and  liberates  ammonia 
from  ammonium  salts.  It  reacts  with  acids  forming  salts  of 
C6H5Hg  — .  It  precipitates  aluminum  hydroxide  from  aluminum  salts.53 
The  hydroxide  is  also  obtained  by  the  oxidation  of  mercury  diphenyl 
with  potassium  permanganate.  The  filtrate  from  manganese  dioxide 
is  an  alkaline  liquid  from  which  the  base  can  be  extracted  by  ben- 
zene.54 

Phenylmercuric  chloride. 
Preparation. 

1.  From  benzene. 

Mercuric  acetate,  glacial  acetic  acid,  and  thiophene-free  benzene 
are  heated  in  a  pressure  flask  for  five  hours  at  100°.  After  cooling 
the  mixture  is  filtered  and  the  residue  is  washed  with  benzene.  This 
residue  consists  of  polymercurated  benzenes  and  mercurous  acetate. 
The  filtrate  and  washings  are  evaporated  to  small  volume  and  treated 
with  alcoholic  calcium  chloride  to  change  the  acetate  to  the  less  solu- 
ble chloride.  The  product  is  washed  with  hot  water.55 

2.  From  benzene  sulfinic  acid. 

When  this  substance  is  heated  with  one  molecule  of  mercuric  chlo- 
ride in  alcohol  until  no  more  sulfur  dioxide  is  evolved  a  small  amount  of 
phenylmercuric  chloride  is  obtained.  It  can  be  separated  from  any 
metallic  mercury  formed  in  the  reaction  by  dissolving  in  pyridine,  fil- 
tering, and  reprecipitating  with  water.56 

3.  From  mercury  diphenyl  and  mercuric  chloride  or  mercurous  chlo- 

ride in  alcohol  or  acetone.57 

4.  From  phenyl  boric  acid  heated  with  mercuric  chloride  and  water.58 

53  Otto,  J.  prakt.  Ctiem.  (2)  1  (1870),  183. 

B*Otto,  J.  prakt.  Chem.  (2)   29  (1884),  136. 

"Boeder  and  Blasi,  Ber.  47   (1914),  2751. 

66  Peters,  Ber.  38  (1905),  2567. 

B7Dreher  and  Otto,  loc.  cit.     Otto,  loc.  cit.     Steinkopf,  Ann.  413   (1917),  313. 

^Michaelis  and  Becker,  Ber.  15    (1882),  182. 


172  COMPOUNDS  OF  MERCURY 

5.  From  triphenyl  stibine  heated  with  mercuric  chloride.59 

6.  From  mercury  diphenyl  and  chlorine.60 

7.  From  mercury  diphenyl  and  hypochlorous  acid  or  chlorine  mon- 
oxide. 

8.  From  mercury  diphenyl  and  thionyl  chloride. 

9.  From  phenylmercuric  hydroxide  and  hydrochloric  acid. 

10.  From  mercury  diphenyl  and  phosphorus  trichloride. 

11.  From  mercury  diphenyl  and  zirconium  chloride.61 

12.  From  mercury  diphenyl  and  silicon  chloride. 

13.  From  mercury  diphenyl  and  stannic  chloride. 

14.  From  mercury  diphenyl  and  antimony  trichloride. 

15.  From  mercury  diphenyl  and  benzene  sulfone  chloride.    Yield  poor. 

16.  From  mercury  diphenyl  and  benzal  chloride. 

Properties. 

Phenylmercuric  chloride  forms  white  satiny  leaflets.  (CHClHg). 
M.P.  251°.  It  is  slightly  soluble  in  hot  alcohol,  benzene,  and  pyridine, 
slightly  soluble  in  ether.  It  sublimes  on  gentle  heating. 

A  number  of  statements  have  been  made  about  this  substance 
which  are  probably  incorrect.62  These  are  that  its  water  solution  has 
an  acid  reaction,  and  that  it  is  soluble  in  bases  and  carbonates  giving 
carbon  dioxide  with  the  latter. 

Reactions. 

1.  Moist  silver  oxide  and  alcohol  give  a  solution  of  phenylmercuric 
hydroxide.63 

2.  Dry  silver  oxide  reacts  with  the  dry  substance  forming  mercury 
diphenyl,  mercuric  oxide,  and  silver  chloride.64    This  is  a  most  unusual 
formation  of  mercury  diphenyl. 

3.  With  arsenic  trichloride.    Phenylmercuric  chloride  reacts  with 
arsenic  trichloride  at  100°  forming  phenyl  dichlorarsine.65    The  state- 
ment that  this  reaction  does  not  take  place  is  untrue.66 

4.  Antimony  trichloride  does  not  react  even  at  200°. 67 

MMichaelis,  Ann.  233  (1886),  49. 

«o  rpne  references  for  this  and  the  following  methods  have  been  given  under 
Mercury  Diphenyl. 

"Peters,  Ber.  41   (1908),  3173. 

«2Dreher  and  Otto,  Ann.  154   (1870),  126. 

«3  Otto,  loc.  cit. 

MOtto,  J.  prakt.  Chem.   (2)   1   (1870),  184. 

«BRoeder  and  Blasi,  Ber.  47   (1914),  2750. 

«« Michaelis,  Ann.  201   (1880),  197,  217. 

«  Boeder  and  Blasi,  loc.  cit.     Michaelis  and  Reese,  Ber.  15   (1882),  2877. 


DERIVED  FROM  AROMATIC  HYDROCARBONS       173 

5.  With    sodium   iodide.     The   only   product   is   itfienylmercuric 
iodide.    No  mercury  diphenyl  is  obtained.    The  cold  acetone  solution 
of  the  chloride  and  sodium  iodide  is  allowed  to  stand  24  hours  and 
poured  into  water.68 

6.  With  iodidechlorides.    The  same  products  are  obtained  as  with 
mercury  diphenyl.69 

7.  With  the  Grignard  reagent.     Benzyl  magnesium  chloride  re- 
acts with  phenylmercuric  chloride  but  gives  dibenzyl  instead  of  any 
of  the  expected  products.70 

8.  With  sulfides.    Ammonium  sulfide  gives  no  action  in  the  cold. 
Long  boiling  with  sodium  sulfide  gives  mercury  diphenyl  and  mercuric 
sulfide.71 

Phenylmercuric  bromide. 
Preparation. 

1.  From  the  Grignard  reagent. 

Phenyl  magnesium  bromide  in  ether  is  treated  with  the  calculated 
amount  of  powdered  mercuric  bromide  in  small  portions  and  then  the 
mixture  is  boiled  for  4  hours.  The  mixture  is  cooled,  decanted,  and 
the  residue  is  boiled  with  three  portions  of  1  per  cent  hydrochloric 
acid  to  remove  any  mercuric  bromide.  The  residue  is  washed  with 
water,  alcohol,  and  ether,  dried  at  100°  and  then  recrystallized  from 
pyridine.  The  pyridine  mother  liquor  is  heated  to  boiling  and  treated 
with  water  to  precipitate  the  rest  of  the  bromide.  Total  yield  93  per 
cent.72 

2.  From  mercury  diphenyl  and  bromine. 

3.  From  mercury  diphenyl  and  mercuric  bromide  in  alcohol  at 
1200.73 

4.  From   ethylene   dibromide   and  mercury   diphenyl   heated   at 
200°. 

Properties. 

Phenylmercuric  bromide  forms  white  rhombic  tablets  of  satiny 
luster.  M.P.  276°  (not  291°). 7*  It  is  insoluble  in  water,  barely  solu- 

88  Steinkopf,  loc.  cit. 

«  Willgerodt,  Ber.  31   (1898),  917. 

L.  W.  Jones,  J.  Am.  Chem.  Soc.  40   (1918),  1268. 

Heumann  and  Kochlin,  loc.  cit. 

Hilpert  and  Gruttner,  Ber.  46   (1913),  1686. 

Dreher  and  Otto,  loc.  cit. 

Otto,  J.  prakt.  Chem.   (2)   1   (1870),  186. 


174  COMPOUNDS  OF  MERCURY 

ble  in  cold  altohol  and  benzene,  more  soluble  on  heating,  and  soluble 
in  hot  pyridine.    It  sublimes  on  careful  heating.    (BrHg) . 

Reactions. 

1.  With  the  Grignard  reagent.    Phenylmercuric  bromide  acts  with 
an  excess  of  phenyl  magnesium  bromide  giving  only  a  40  per  cent 
yield  of  mercury  diphenyl.75    An  excess  of  benzyl  magnesium  bromide 
gives  mercury  dibenzyl  instead  of  the  expected  "mixed"  compound, 
C6H5  — Hg  — CH2  — C6H5.76 

2.  With  ethylene  dibromide.     No  reaction  takes  place  even  in 
sealed  tubes  at  250°. 77 

Phenylmercuric  iodide. 
Preparation. 

1.  From  mercury   diphenyl   and  mercuric   iodide   in   alcohol   at 
120°  ,78    This  reaction  can  be  brought  about  by  simply  refluxing  the 
substances  in  alcohol  until  the  red  color  of  the  mercuric  iodide  has  dis- 
appeared.   The  phenylmercuric  iodide  obtained  is  practically  pure.79 

2.  From  mercury  diphenyl  and  iodine  in  carbon  disulfide. 

3.  From  phenylmercuric  cyanide  and  iodine.80 

Properties. 

Phenylmercuric  iodide  forms  rhombic  tablets  of  satiny  luster.  (I). 
It  is  unchanged  by  light.  M.P.  266°.  It  is  insoluble  in  water,  almost 
insoluble  in  cold  alcohol,  ether,  and  benzene,  more  soluble  hot,  soluble 
in  chloroform,  and  still  more  so  in  carbon  disulfide.  Gentle  heating 
sublimes  part  of  the  substance  and  decomposes  the  rest  giving  mer- 
curic iodide.  The  other  products  have  not  been  identified.81 

Reactions. 

1.  With  sodium  amalgam.  Phenylmercuric  iodide  reacts  with  so- 
dium amalgam  in  dry  benzene  or  even  in  alcohol  giving  mercury  di- 
phenyl. Metallic  sodium  gives  sodium  amalgam,  sodium  iodide,  and  a 
brown  insoluble  product  which  is  probably  sodium  phenyl.82 

"  Hilpert  and  Gruttner,  loc.  cit.  1679. 
"Hilpert  and  Gruttner,  Ber.  48   (1915),  907. 
"  Dreher  and  Otto,  loc.  cit.  129. 
"Dreher  and  Otto,  loc.  cit. 

79  Whitmore,  unpublished  results. 

80  Otto,  J.  prakt.  Chem.  (2)  1   (1870),  182. 

81  Dreher  and  Otto,  loc.  cit.  109. 

»2  Dreher  and  Otto,  loc.  cit.  93,  115. 


DERIVED  FROM  AROMATIC  HYDROCARBONS       175 

2.  With  iodine.  The  reaction  in  alcohol  or  carbon  disulfide  gives 
phenyl  iodide  and  mercuric  iodide. 

Phenylmercuric  formate. 

Mercury  diphenyl  is  dissolved  in  hot  concentrated  formic  acid  and 
the  solution  is  poured  into  water.  The  precipitate  is  recrystallized 
from  hot  formic  acid.  Small  glassy  tablets.  M.P.  171°. 

Phenylmercuric  acetate,  Acetoxymercuribenzene. 
Preparation. 

1.  From  mercury  diphenyl  and  glacial  acetic  acid. 

2.  From  mercury  diphenyl  and  mercuric  acetate  in  alcohol  at 
120°. 

3.  From  phenylmercuric  iodide  and  silver  acetate  in  cold  alcohol. 

4.  From  benzene  by  direct  mercuration. 

Mercuric  acetate  does  not  react  with  boiling  benzene.  The  two  sub- 
stances react  when  heated  to  100-110°.  The  acetate  is  hard  to  purify 
and  is  usually  converted  to  the  less  soluble  chloride.83 

Properties. 

Phenylmercuric  acetate  forms  small,  white  rhombic  prisms  of 
glassy  luster.  M.P.  149°.  It  is  little  soluble  in  cold  water,  more  solu- 
ble hot,  soluble  in  glacial  acetic  acid,  benzene,  and  alcohol.  It  can  be 
recrystallized  from  water  or  alcohol. 

Reactions. 

1.  On  heating.    Heating  at  150°  decomposes  phenylmercuric  ace- 
tate with  the  formation  of  carbon,  mercury,  benzene,  acetic  anhydride, 
acetic  acid,  and  diphenyl.84 

2.  With  acids.    Boiling  with  hydrochloric  acid  or  dilute  sulfuric 
acid  gives  benzene  and  mercuric  salts. 

3.  With  sodium  amalgam.    In  the  presence  of  water  the  products 
are  mercury,  benzene,  and  sodium  acetate.  , 

4.  With  halogens.    An  aqueous  solution  warmed  with  iodine  gives 
mercuric  iodide,  phenyl  iodide,  and  acetic  acid.    Some  iodine  pentoxide 
is  also  formed.85 

5.  With  sulfides.    Aqueous  or  alcoholic  solutions  treated  with  hy- 
drogen sulfide  give  a  heavy  white  precipitate  of   (C6H5Hg)2S  which 

83  See  under  preparation  of  Phenylmercuric  chloride, 

84  Dreher  and  Otto,  loc.  cit.  122. 
8sJ>reher  and  Otto,  loc.  cit.  120, 


176  COMPOUNDS  OF  MERCURY 

turns  gray  and  then  black  on  standing.     Ammonium  sulfhydrate  in 
tubes  at  100°  gives  mercuric  sulfide,  benzene,  and  acetic  acid. 

6.  With  sulfur.    Heating  phenylmercuric  acetate  with  sulfur  forms 
mercuric  sulfide,  benzene,  acetic  acid,  acetic  anhydride,  diphenyl  sul- 
fide, and  a  crystalline  sulfur  compound  of  unknown  composition.86 

7.  With  arsenic  trichloride.    The  acetate  acts  as  well  as  the  chlo- 
ride forming  phenyl  dichlorarsine.87 

8.  With  sodium  stannite.    A  suspension  of  the  acetate  in  water 
reacts  with  sodium  stannite  solution  forming  mercury  diphenyl  and 
metallic  mercury.88 

Phenylmercuric  propionate. 

Mercury  diphenyl  is  dissolved  in  hot  propionic  acid.  The  benzene 
formed  is  distilled  off.  The  mixture  is  then  poured  into  dilute  sodium 
carbonate  solution.  The  precipitate  is  recrystallized  from  hot  water.  It 
is  practically  insoluble  in  cold  water  but  is  soluble  in  alcohol  and  ben- 
zene. M.P.  166°  after  softening  slightly  at  145°. 

Phenylmercuric  myristate,  C6H5 —  Hg  —  0 — CO  —  C13H27. 

Myristic  acid,  mercury  diphenyl,  and  alcohol  are  heated  to  120°. 
The  product  forms  small  fatty  rhombic  plates  which  are  insoluble  in 
water  but  soluble  in  hot  alcohol  and  benzene.  Boiling  hydrochloric 
acid  changes  the  compound  to  mercuric  chloride,  benzene,  and  my- 
ristic  acid. 

Phenylmercuric  cyanide. 

Mercuric  cyanide  and  mercury  diphenyl  heated  in  alcohol  at  120° 
form  long  fine  rhombic  prisms  which  are  slightly  soluble  in  hot  water 
and  more  soluble  in  hot  alcohol  and  benzene.  M.P.  204°.  Phenyl- 
mercuric cyanide  can  also  be  prepared  from  the  iodide  and  silver  cy- 
anide. Heated  with  hydrochloric  acid  at  120°  the  cyanide  gives  ben- 
zene, mercuric  chloride,  formic  acid,  and  ammonium  chloride.  Alco- 
holic potassium '  hydroxide  at  120°  gives  metallic  mercury,  benzene, 
and  potassium  cyanate.  Iodine  gives  phenylmercuric  iodide  and  cy- 
anogen iodide.  Hydrogen  sulfide  first  gives  a  white  precipitate  and 
then  mercuric  sulfide,  hydrocyanic  acid  and  benzene.  No  sulfocyanate 
is  formed  by  heating  with  sulfur. 

86  Dreher  and  Otto,  loc.  cit.  124. 

87  Boeder  and  Blasi,  Ber.  47   (1914),  2752. 
I8  Dimroth,  Chem.  Zentr.  1901  I  45p. 


DERIVED  FROM  AROMATIC  HYDROCARBONS       177 

Phenylmercuric  sulfide. 

The  sulfide  is  prepared  from  phenylmercuric  chloride  and  the  cal- 
culated amount  of  sodium  sulfide  in  alcohol.  When  heated  it  de- 
composes to  mercuric  sulfide  and  mercury  diphenyl.89 

Phenylmercuric  nitrate. 
Preparation. 
It  cannot  be  made  from  mercury  diphenyl  and  nitric  acid. 

1.  From  phenylmercuric  chloride  and  silver  nitrate  in  alcohol. 

2.  From  mercury  diphenyl  and  mercuric  nitrate. 

3.  From  mercury  diphenyl  and  nitrogen  trioxide.90 

Properties. 

Phenylmercuric  nitrate  forms  rhombic  tablets,  insoluble  in  cold 
water,  slightly  soluble  hot,  more  soluble  in  hot  alcohol  and  benzene. 
M.P.  176-186°. 

Phenylmercuric  sulfocyanate. 
Preparation. 

1.  From  mercury  diphenyl  and  mercuric  sulfocyanate  heated  in 
alcohol  at  120°. 

2.  Phenylmercuric  iodide  and  thiocyanogen,  (SCN)2,  form  phenyl- 
mercuric thiocyanate  and  iodine.91  , 

Properties. 

Phenylmercuric  sulfocyanate  forms  small  silky  tablets,  insoluble 
in  water,  soluble  in  hot  alcohol  and  benzene.  M.P.  231-232.5°  (NSHg) . 

Phenylmercuric  carbonate. 

Phenylmercuric  chloride  in  alcohol  is  treated  with  silver  car- 
bonate. The  product  forms  fine  white  needles  which  are  very  little 
soluble  in  hot  water,  but  fairly  soluble  in  hot  alcohol  and  ether.  It 
decomposes  on  heating.  Acetic  acid  liberates  carbon  dioxide. 

Compounds  of  di(phenylmercuri)  ammonium,  (C6H5Hg)2NH2 — . 92 
Di(phenylmercun)  ammonium  acetate,  (C6H5Hg)  2NH2OAc. 

Phenylmercuric  acetate  is  dissolve'd  in  ammonium  hydroxide.    On 

89Pesci,  Gaze.  chim.  ital.  29  I   (1899)   394.     Z.  anorg.  Ch-em.  32   (1902),  230. 

90  Bambe'rger,  Ber.  30  (1897),  510. 

81  Soderback,  Ann.  419   (1919),  268. 

B2Pesci,  Gaez.  chim.  ital.  39  I   (1909),  148  ff. 


178  COMPOUNDS  OF  MERCURY 

standing  colorless  laminae  separate.  The  complex  acetate  is  very  solu- 
ble in  alcohol,  especially  on  heating,  little  soluble  in  water,  and  in- 
soluble in  benzene  and  chloroform.  The  solution  is  alkaline  and  caustic 
to  the  skin.  M.P.  179°  (CHNHg).  The  acetate  reacts  with  an  excess 
of  concentrated  sodium  thiosulfate  giving  mercury  diphenyl.  Reflux- 
ing  with  carbon  disulfide  in  alcohol  gives  the  same  product.  The  cor- 
responding complex  nitrate  is  prepared  by  dissolving  phenylmercuric 
acetate  in  ammonium  hydroxide  and  adding  a  concentrated  solution  of 
ammonium  nitrate.  The  precipitate  is  recrystallized  from  hot  alcohol. 
(NHg).  It  forms  very  small  colorless  laminse.  It  dissolves  very 
slightly  in  water  giving  an  alkaline  reaction.  M.P.  230-235°  with  de- 
composition. The  sulfate  is  prepared  the  same  as  the  nitrate  but 
sodium  sulfate  is  used  as  the  precipitating  agent  as  the  complex  sulfate 
forms  a  double  compound  with  ammonium  sulfate.  The  complex  sul- 
fate forms  white  crystals  which  are  slightly  soluble  in  water  giving  an 
alkaline  reaction.  (Hg,S04).  It  does  not  melt.  The  double  salt  con- 
tains one  molecule  of  ammonium  sulfate.  (NHg,S04).  The  chloride 
is  obtained  by  cooling  a  filtered  solution  of  phenylmercuric  chloride  in 
hot  ammonium  hydroxide.  The  crystals  which  form  are  slightly  solu- 
ble in  water  with  an  alkaline  reaction.  (Hg) .  M.P.  184°  with  decom- 
position. 

Tetra(phenylmercuri)  thiourea,  (C6H5Hg)4N2CS. 

Phenylmercuric  acetate  dissolved  in  ammonium  hydroxide  is  treated 
with  the  calculated  amount  of  thiourea  in  water  solution.  The  white 
amorphous  precipitate  is  carefully  washed  and  air  dried.  (NSHg) .  It 
blackens  at  105°  but  does  not  melt.  Boiled  with  alcohol  it  gives  mer- 
curic sulfide,  mercury  diphenyl,  and  di(phenylmercuri)  cyanamide, 
(C6H5Hg)2N-CN. 

Di(phenylmercuri)  cyanamide. 

It  is  prepared  as  just  described  or  by  mixing  an  alcoholic  solution 
of  phenylmercuric  acetate  with  an  aqueous-alcoholic  solution  of  cy- 
anamide. The  white  amorphous  precipitate  is  insoluble  in  common 
solvents.  It  decomposes  without  melting.  When  heated  on  platinum 
foil  it  deflagrates  slightly.  Cold  dilute  hydrochloric  acid  gives  a 
solution  of  cyanamide  and  a  residue  of  phenyl  mercuric  chloride. 


DERIVED  FROM  AROMATIC  HYDROCARBONS        179 

Tolylmer curie  Compounds. 

o-Mercury  Ditolyl. 
Preparation. 

1.  Small  amounts  of  the  ortho  compound  are  obtained  from  the 
benzene  mother  liquors  of  the  product  of  the  action  of  1.5  per  cent 
sodium  amalgam  and  ethyl  acetate  on  impure  bromotoluene.93 

2.  Pure  o-bromotoluene  (from  'o-toluidine)  is  mixed  with  xylene 
and  ethyl  acetate  and  refluxed  for  six  hours  with  twice  the  calculated 
amount  of  8  per  cent  sodium  amalgam.    Yield  33  per  cent.94 

Properties.95 

o-Mercury  ditolyl  forms  white  tablet  crystals  which  are  soluble 
in  hot  benzene.    (HHg).    M.P.  107°  (108°).    B.P.  219°  at  14  mm. 

Reactions. 

1.  With  boron  trichloride  in  a  tube  at  180°  for  12  hours  it  gives 
o-tolylboron  dichloride  and  mercuric  chloride.96 

2.  Zirconium  chloride  gives  no  reaction  either  dry  or  in  presence 
of  moisture.97 

3.  A  large  excess  of  phosphorus  trichloride  at  190°  gives  mercuric 
chloride  and  o-tolyl  dichlorophosphine.98 

4.  Arsenic  trichloride  gives  o-tolyl  dichlorarsine." 

5.  Nitrogen  tetroxide  at  0°  acts  on  a  chloroform  solution  of  o-mer- 
cury   ditolyl   giving  o-tolylmercuric   nitrate   and   o-nitrosotoluene.10T) 
Nitrogen  trioxide  gives  o-tolylmercuric  nitrate,  toluene  o-diazonium 
nitrate,  and  a  very  little  of  the  nitroso  compound. 

o-Tolylmercuric  chloride. 
Preparation. 

1.  From   o-tolylboric   acid  boiled  with   mercuric   chloride   solu- 
tion.101 

2.  From  the  benzene  mother  liquors  from  the  para  compound  pre- 

93  Ladenberg,  Ann.  173  (1874),  165.    Michaelis  and  LaCoste,  Ann.  201  (1880),  247. 
84  Michaelis,  Ann.  293   (1896),  292. 

95  Michaelis,  Ber.  27  (1894),  247.     Zeiser,  Ber.  28  (1895),  1670.     Ladenberg,  loc.  cit. 
98  Michaelis,  loc.  cit. 

97  Peters,  Ber.  41   (1908),  3173. 

88  Michaelis,  Ann.  293  (1896),  292. 

98  Michaelis  and  LaCoste,  loc.  cit. 
100Kunz,  Ber.  31   (1898),  1530. 
^Michaelis,  Ber.  27  (1894),  247. 


180  COMPOUNDS  OF  MERCURY 

pared  by  treating  toluene  with  mercuric  acetate  and  precipitating 
with  sodium  chloride  solution.  The  o-  and  p-  compounds  formed  in 
this  way  are  hard  to  separate  completely.102 

3.     By  treating  a  solution  of  the  nitrate  with  a  chloride  solution.103 

Properties. 

White  crystals  from  alcohol.     (CHHg).    M.P.  146°. 
Reactions. 

A  solution  of  the  chloride  in  chloroform  reacts  with  bromine  giv- 
ing a  product  which  on  oxidation  gives  o-bromobenzoic  acid.104 

o-Tolylmer curie  nitrate. 

The  nitrate  is  prepared  from  o-mercury  ditolyl  and  the  oxides  of 
nitrogen  as  described  above.  It  is  soluble  in  water.  Chloride  solu- 
tions precipitate  o-tolylmercuric  chloride. 

m-Mercury  Ditolyl. 

m-Bromotoluene  is  treated  with  3  per  cent  sodium  amalgam  in  the 
usual  way.105  The  m-mercury  ditolyl  forms  colorless  or  light  yellow 
needles.  (CHHg).  M.P.  102°.  It  is  soluble  in  cold  benzene,  chloro- 
form, acetone,  ethyl  acetate,  difficultly  soluble  in  alcohol,  ether,  and 
low  boiling  ligroin.  It  is  best  recrystallized  from  ethyl  acetate.  When 
heated  with  phosphorus  trichloride  for  12  hours  at  200°  it  gives 
m-tolylmercuric  chloride  and  m-tolyl  dichlorophosphine. 

m-Tolylmercuric  chloride. 
Preparation. 

1.  From  m-tolyl  boric  acid  heated  with  a  concentrated  mercuric 
chloride  solution.106 

2.  From  m-mercury  ditolyl  and  mercuric  chloride  in  alcohol. 

3.  From  m-mercury  ditolyl  and  phosphorus  trichloride. 

Properties. 

m-Tolylmercuric  chloride  forms  white  clustered  needles.  (CHC1). 
M.P.  160°.  It  is  easily  soluble  in  chloroform  and  benzene,  but  diffi- 
cultly soluble  in  alcohol.  It  sublimes  on  gentle  heating. 

102Dimroth,  Ber.  32  (1899),  761. 
10S  Kunz,  loc.  cit. 
lo4Dimroth,  loc.  cit. 

105  Michaelis,  Ber.  28  (1895),  589.     Ann.  293   (1896),  303. 
•   10«Khotinsky  and  Melamed,  Ber.  42   (1909),  3094. 


DERIVED  FROM  AROMATIC  HYDROCARBONS       181 

m-Tolylmer curie  bromide. 

The  ditolyl  compound  is  treated  with  mercuric  bromide  in  alcohol. 
It  is  recrystallized  from  a  large  volume  of  hot  alcohol.  (Br) .  It  forms 
long  white  needles.  M.P.  184°. 

m-Toly  Inter  curie  iodide. 

It  is  prepared  like  the  bromide.  (I).  It  forms  white  pearly  leaflets. 
M.P.  162°. 

m-Tolylmercuric  salts  of  organic  acids. 

These  salts  are  prepared  by  dissolving  m-mercury  ditolyl  in  the 
proper  acid  by  heating  and  then  diluting  the  solution  with  water.  The 
formate  forms  long  white  needles  which  melt  at  106°.  (CH).  The  ace- 
tate is  similar  to  the  formate.  It  forms  white  needles  which  are  diffi- 
cultly soluble  in  cold  water  but  readily  soluble  in  hot  water  or  alcohol. 
M.P.  84°.  The  propionate  forms  long  white  needles  which  are  insolu- 
ble in  cold  water,  slightly  soluble  in  hot,  easily  soluble  in  alcohol.  (CH) . 

p-Mercury  Ditolyl. 
Preparation  and  properties. 

p-Bromotoluene  is  treated  with  sodium  amalgam  in  the  usual 
way.107  The  product  forms  needle  crystals  which  are  insoluble  in 
water,  slightly  soluble  in  cold  alcohol,  more  soluble  in  hot  benzene, 
chloroform,  and  carbon  disulfide.  (CHHg).  M.P.  238°.  When  heated 
under  diminished  pressure  it  sublimes.108 

The  best  method  for  preparing  p-mercury  ditolyl  makes  use  of  the 
method  of  Peters  for  changing  sulfinic  acids  to  aromatic  —  HgCl  com- 
pounds. p-Toluene  sulfone  chloride,  obtained  as  a  by-product  in  the 
saccharin  industry,  is  changed  to  the  sulfinic  acid  in  the  usual  way. 
This  is  boiled  with  alcoholic  mercuric  chloride  to  form  p-tolylmercuric 
chloride.  This  substance  can  be  converted  to  p-mercury  ditolyl  by 
the  reagents  which  usually  change  RHgX  to  R2Hg.  The  best  yields 
are  obtained  with  potassium  sulfocyanate.  Even  potassium  iodide 
gives  a  better  yield  than  sodium  thiosulfate.109  This  series  of  reactions 
is  the  easiest  method  for  obtaining  a  compound  of  the  type  R2Hg  in 
which  R  is  an  aromatic  hydrocarbon  residue  as  the  yields  are  excellent. 

107Dreher  and  Otto,  Ann.  154  (1870),  171.  Wurtz,  Compt.  rend.  68  (1870),  1298. 
Ann.  Spl.  7  (1870),  128.  Mlchaelis  and  La  Coste,  Ann.  201  (1880),  246. 

108  Ladenberg,  Ann.  173   (1874),  162.     Zeiser,  Ber.  28   (1895),  1670. 

109  Unpublished  results,  Whitmore  and  L.  F.  Howe. 


182  COMPOUNDS  OF  MERCURY 

Reactions. 

1.  The  vapors  of  p-mercury  ditolyl  passed  through  a  hot  tube  give 
carbon,  toluene,  metallic  mercury,  and  an  oil  which  may  be  impure 
ditolyl.110 

2.  Mercuric  chloride  gives  p-toly Imercuric  chloride. 

3.  Hot  aqueous  potassium  permanganate  gives  manganese  dioxide 
and  an  alkaline  solution  which  reacts  with  dilute  hydrochloric  acid 
giving  p-tolylmercuric  chloride.111 

4.  Nitrogen  trioxide  in  chloroform  gives  p-tolylmercuric  nitrate, 
p-toluene  diazonium  nitrate,  and  a  small  amount  of  p-nitroso  toluene. 
Pure  nitric  oxide  gives  no  reaction.    Nitrogen  tetroxide  gives  p-tolyl- 
mercuric nitrate  and  p-nitroso  toluene.112 

5.  Boron  trichloride  gives  p-tolyl  boron  dichloride.113 

6.  Halogens  give  the  corresponding  organomercuric  halides  and 
p-tolyl  halides. 

7.  Boiling  mineral  acids  give  toluene  and  mercuric  salts.     Con- 
centrated nitric  acid  gives  nitrotoluenes  instead  of  the  hydrocarbon 
itself.114 

8.  Silicon  tetrachloride  at  300°  gives  p-tolyl  silicon  trichloride.115 

9.  Arsenic  trichloride  gives  p-tolyl  dichlorarsine.116 

p-Toly Imercuric  chloride. 
Preparation. 

1.  From  p-toluene  sulfinic  acid  heated  with  mercuric  chloride  un- 
til no  more  sulfur  dioxide  is  evolved.117 

2.  p-Toluene  sulfone  chloride  heated  with  mercury  diphenyl  for 
15  hours  at  120°  gives  a  good  yield  of  p-tolylmercuric  chloride.118    This 
peculiar  reaction  has  not  been  studied  in  any  detail. 

3.  From  p-tolyl  boric  acid  heated  with  mercuric  chloride  solu- 
tion.119 

4.  Toluene  reluxed  a  short  time  with  mercuric  acetate  and  treated 
with  sodium  chloride  solution  gives  a  mixture  of  the  o-  and  p-  com- 

10Dreher  and  Otto,  loc.  cit. 

"Otto,  J.  prakt.  Chem.   (2)   1   (1870),  185. 

"Kunz,  Bcr.  31  (1898),  1528. 

13  Michaelis  and  Becker,  Ber.  15   (1882),  185. 

14  Dreher  and  Otto,  loc.  cit. 

'"Ladenburg,  Ann.   173    (1874),  162.  V 

"Michaelis  and  La  Coste,  loc.  cit.     Michaelis,  Ann.  320   (1902),  301. 
"Peters,  Ber.  38   (1905),  2569. 

18  Otto,  Ber.  18  (1885),  249. 

19  Michaelis  and  Becker,  loc.  cit. 


DERIVED  FROM  AROMATIC  HYDROCARBONS       183 

pounds  which  can  be  separated  only  by  repeated  crystallizations  from 
benzene.120 

5.  From  p-tolylmercuric  nitrate  and  hydrochloric  acid.121 

6.  From  the  action  of  hydrochloric  acid  on  p-tolylmercuric  hy- 
droxide formed  by  oxidizing  p-mercury  ditolyl  with  potassium  perman- 
ganate.122 

7.  From  p-mercury  ditolyl  and  mercuric  chloride.123 

Properties. 

p-Tolylmercuric  chloride  forms  silky  rhombic  tablets.  It  is  insolu- 
ble in  water  and  ether,  difficultly  soluble  in  hot  alcohol,  more  easily 
in  hot  benzene,  chloroform,  acetone,  and  pyridine.  (CHHg).  M.P. 
233°  (not  187°). 124 

Reactions. 

1.  With    halogens.     Bromine   gives   p-bromotoluene    melting   at 
28.50.125 

2.  With  sodium  iodide.    In  cold  acetone  solution  the  only  product 
is  p-tolylmercuric  iodide.    No  p-mercury  ditolyl  is  formed.126 

p-Tolylmercuric  bromide. 

p-Tolyl  magnesium  bromide  is  heated  with  mercuric  chloride.127 
It  is  soluble  in  chloroform,  alcohol,  benzene,  insoluble  in  cold  carbon 
disulfide,  slightly  on  heating.  It  forms  thin  scales  of  a  pearly  gray 
luster.  (Br).  M.P.  228°.  It  reacts  with  phenyl  dichlorophosphine  at 
270°  giving  phenyl  p-tolyl  chlorophosphine.128 

p-Tolyl  mercuric  iodide. 

The  iodide  is  prepared  by  treating  p-tolylmercuric  chloride  with 
sodium  iodide  or  by  treating  p-mercury  'ditolyl  with  iodine.129  It 
forms  white  satiny  rhombic  tablets.  M.P.  220°.  It  is  insoluble  in 
water,  slightly  soluble  in  hot  alcohol,  more  soluble  in  hot  benzene.  It 
sublimes  on  careful  heating. 

"ODimroth,  Ber.  32  (1899),  761.     Steinkopf,  Ann.  413  (1917),  329. 

121  Kunz,  loc.  cit. 

122  Otto,  J.  prakt.  Cnem.   (2)   29   (1884),  138. 

123  Otto,  J.  prakt.  Chem.   (2)   1   (1870),  185. 

124  Otto,  Ber.  18   (1885),  249. 
'28Dimroth,  Ber.  32  (1899),  761. 

128  Steinkopf,  Ann.  413   (1917),  329. 

127  Pope  and  Gibson,  J.  Chem.  800.  101   (1912),  736. 

128  Pope  and  Gibson,  loc.  cit. 

128  Steinkopf,  loc.  cit.     Dreher  and  Otto,  Ann.  154   (1870),  173. 


184  COMPOUNDS  OF  MERCURY 

p-Tolyl  mercuric  nitrate. 

p-Mercury  ditolyl  is  dissolved  in  chloroform  and  treated  with  the 
trioxide,  or  tetroxide  of  nitrogen.  M.P.  187°,  not  sharp. 

p-Tolylmer curie  acetate. 
Preparation. 

1.  From  heating  toluene  and  mercuric  acetate.    The  product  is 
not  isolated  but  is  transformed  to  the  chloride.180 

2.  From  p-mercury  ditolyl  and  glacial  acetic  acid. 

Properties. 

p-Tolylmercuric  acetate  forms  small  white  glassy  rhombic  prisms. 
M.P.  153°.  It  is  practically  insoluble  in  cold  water,  slightly  soluble  in 
hot  water,  more  soluble  in  alcohol,  carbon  disulfide,  and  benzene. 

Reactions. 

It  reacts  like  phenylmercuric  acetate  with  inorganic  acids,  iodine 
and  hydrogen  sulfide. 

Benzyl  Mercury  Compounds. 

Mercury  Dibenzyl. 
Preparation. 

Considerable  difficulty  was  experienced  in  making  this  substance.131 
The  only  method  which  gives  it  is  the  action  of  a  Grignard  reagent 
with  mercuric  compounds. 

1.  From  benzyl  magnesium  chloride  and  mercuric  chloride.132 

2.  From  benzyl  magnesium  chloride  and  benzyl  mercuric  chlo- 
ride.133 

3.  Benzyl  magnesium  bromide  reacts  with  phenyl  mercuric  bro- 
mide giving  mercury  dibenzyl  instead  of  the  expected  product.134 

Properties. 

Mercury  dibenzyl  forms  long  brittle  colorless  needles.  (CHHg) .  It 
is  easily  soluble  in  alcohol,  ether,  chloroform,  carbon  disulfide,  acetic 

13°Dimroth,  loc.  cit.     Ber.  31  (1898),  2154.     Chem.  Zentr.  1901  I  450. 

181  Campisi,  Compt.  rend.  61    (1865),  861.     Wurtz,  Oompt.  rend.  68   (1869),  1300. 
Dreher  and  Otto,  Ann.  154   (1870),  176. 

182  Pope  and    Gibson,   loc.    cit.      Wolff,   Ber.    46    (1913),    64.      Jones   and    Werner, 
J.  Am.  Chem.  8oc.  40   (1918),  1266. 

188  Jones  and  Werner,  loc.  cit. 

184Hilpert  and  Griittner,  Ber.  48  (1915),  907. 


DERIVED  FROM  AROMATIC  HYDROCARBONS       185 

acid,  benzene  and  ethyl  acetate,  but  difficultly  soluble  in  high-  and 
low-boiling  ligroin.  It  has  a  sweet  nauseating  odor. .  It  gives  no 
absorption  bands.  In  this  remarkable  transparence  it  resembles  mer- 
cury diphenyl.135 

Reactions. 

1.  Glacial  acetic  acid  at  170°  for  7  hours  gives  mercury,  toluene, 
dibenzyl  and  benzyl  acetate.136 

2.  Mercury  dibenzyl  reacts  quantitatively  with  alcoholic  solutions 
of  mercuric  acetate  and  mercuric  chloride  giving  benzylmercuric  ace- 
tate and  chloride  respectively. 

3.  Heating  at  170°  gives  mercury  and  dibenzyl. 

Benzylmercuric  chloride. 
Preparation. 

1.  From  benzyl  magnesium  chloride  and  an  excess  of  mercuric 
chloride. 

2.  From  mercury  dibenzyl  and  alcoholic  mercuric  chloride. 

3.  From  benzyl  boric  acid  and  aqueous  mercuric  chloride.137 

Properties. 

Benzylmercuric  chloride  forms  white  lustrous  leaflets.     (CHC1). 
M.P.  104°.    It  is  best  recrystallized  from  alcohol. 

Reactions. 

1.  Heat  decomposes  it. 

2.  With  the  Grignard  reagent.    Benzyl  magnesium  chloride  reacts 
giving  a  good  yield  of  mercury  dibenzyl.    It  does  not  react  with  phenyl 
magnesium  bromide.138 

Benzylmercuric  bromide. 

Mercury  dibenzyl  in  alcohol  is  treated  with  mercuric  bromide. 
Leaflets.     (Br).    M.P.  119°. 

Benzylmercuric  iodide. 

It  is  prepared  like  the  bromide  and  has  similar  properties.    M.P. 
117°   (I). 

'"Purvis  and  McClelland,  J.  Chem.  Soc.  101  (1912),  1514. 

i»«  pope  and  Gibson,  loc.  cit.     Jones  and  Werner,  loc.  cit.     Kharasch,  J.  Am.  Chem. 
Soc.  43  (1921),  May  ? 

'"Khotinsky  and  Melamed,  Ber.  42  (1909),  3095. 

188  Jones  and  Werner,  J.  Am.  Chem.  Soc.  40  (1918),  1266. 


186  COMPOUNDS  OF  MERCURY 

Benzylmer curie  acetate. 
Preparation. 

1.  From  mercury  dibenzyl  and  mercuric  acetate  in  alcohol. 

2.  From  benzylmercuric  chloride  and  silver  acetate  in  alcohol. 

Properties. 

Benzylmercuric  acetate  forms  long  white  needle  crystals  from 
alcohol.  (CH).  M.P.  126°. 

Reactions. 

Heating  with  glacial  acetic  acid  for  7  hours  at  170°  gives  metallic 
mercury  and  benzyl  acetate  as  the  only  products.139 

Benzylmercuric  cyanide. 

Mercury  dibenzyl  is  heated  with  alcoholic  mercuric  cyanide  in  a 
tube  at  130°.  The  product  forms  fine  soft  white  needles.  (CH) .  M.P. 
124°. 

Mercury  Derivatives  of  Xylenes  and  Higher  Benzene  Homologs. 

Mercuribis-3,  4-dimethyl-  benzene. 

This  substance  is  obtained  as  a  by-product  in  the  action  of  the 
corresponding  bromoxylene  with  chloroformic  ester  and  sodium  amal- 
gam. It  is  difficultly  soluble  in  ether  and  hot  alcohol,  easily  soluble 
in  chloroform,  carbon  disulfide,  and  benzene.  It  is  best  crystallized 
from  hot  ether  or  alcohol  from  which  it  separates  as  long  fine  silky 
needles.  M.P.  150°.  It  sublimes  on  careful  heating.140 

Mercuribis-2,  4-dimethyl  benzene. 

The  corresponding  bromoxylene  is  treated  with  2  per  cent  sodium 
amalgam.  It  crystallizes  from  benzene  in  felted  needles.  M.P.  170°. 
It  is  difficultly  soluble  in  ether  and  alcohol,  easily  soluble  in  hot  ben- 
zene. It  does  not  react  with  phosphorus  trichloride  up  to  180°.  At 
230°  the  mixture  blackens  giving  some  of  the  corresponding  xylyl  di- 
chlorophosphine  and  2,  4-dimethylphenylmercuric  chloride.141  It  re- 
acts with  arsenic  trichloride  forming  2,  4-dimethylphenyl  dichlorar- 
sine.142 

139  Jones  and  Werner,  loc.  cit. 

l4°Jacobson,  Ber.  17   (1884),  2374. 

^Weller,  Ber.  20   (1887),  1719.     Michaelis,  Ann.  293   (1896),  313. 

142  Michaelis,  Ann.  320   (1902),  330. 


DERIVED  FROM  AROMATIC  HYDROCARBONS       187 

Mercuribis-2,  5-dimethyl  benzene. 

This  substance  is  formed  as  a  by-product  in  the  action  of  the  cor- 
responding bromoxylene  with  sodium  amalgam  and  chloroformic  ester 
at  110°.  It  is  insoluble  in  water,  difficultly  soluble  in  ether  and  hot 
alcohol,  very  soluble  in  chloroform,  carbon  disulfide,  and  benzene.  It 
is  best  crystallized  from  hot  toluene.  It  forms  hard  transparent 
prisms.  M.P.  123°.  It  turns  yellow  in  light.  Distillation  gives  mer- 
cury and  di-p-xylene.  It  reacts  in  the  usual  way  with  arsenic  tri- 
chloride at  230°. 143 

Mercuribis-2,  4,  6-trimethylbenzene. 

The  corresponding  bromide,  bromomesitylene,  is  treated  with  so- 
dium amalgam  in  the  usual  way.  It  forms  silvery  needles  which  are 
fairly  soluble  in  benzene  but  very  difficultly  soluble  in  alcohol.  M.P. 
236°.  It  reacts  with  mercuric  halides  on  heating  giving  the  2,  4,  6-tri- 
methylphenylmercuric  halides.  All  form  long  colorless  needles.  The 
melting  points  are:  Chloride  200°,  bromide  194°,  iodide  1780.144 

Mercuribis-2,  4>  5-trimethylbenzene.*44& 

2,  4,  5-Trimethylphenyl  bromide  is  treated  with  1.5  per  cent  so- 
dium amalgam.  It  forms  white  prisms.  M.P:  189°.  It  is  easily  soluble 
in  benzene,  chloroform,  carbon  disulfide,  insoluble  in  cold  alcohol,  diffi- 
cultly soluble  in  hot  alcohol.  It  reacts  with  mercuric  halides  giving 
the  2,  4,  5-trimethylphenylmercuric  halides  which  are  obtained  as  fine 
white  needles.  The  melting  points  are:  chloride  201°,  bromide  211°, 
iodide  196-7°. 

Mercuribis-pentamethylbenzene. 

Pentamethylphenyl  bromide  is  treated  with  sodium  amalgam  in  the 
usual  way.  The  product  is  insoluble  in  alcohol,  difficultly  soluble  in 
ether,  easily  soluble  in  hot  xylene.  It  forms  small  prisms.  M.P.  266°. 
Heating  to  a  higher  temperature  causes  decomposition.145 

Mercuribis-4-propylbenzene. 

4-n-propylphenyl  bromide  reacts  with  1  per  cent  sodium  amalgam 
giving  a  very  poor  yield  of  the  mercury  compound.  It  crystallizes 
from  benzene  or  alcohol  in  long  shiny  needles.  (CH).  M.P.  110°.146 

"»  Michaelis,  ibid. 

144 Michaelis,  Ber.  28  (1895),  591. 

J"a  Ibid. 

145  Jacobson,  Ber.  22   (1889),  1220. 

"8R.  Meyer,  J.  prakt.  CJwm.  (2)   34  (1886),  103. 


188  COMPOUNDS  OF  MERCURY 

Mercuribis-2-methyl-5-isopropylbenzene,  Mercuribis-p-cymene. 

The  bromide  of  p-cymene  is  treated  with  sodium  amalgam  in  the 
usual  way.  The  product  crystallizes  from  alcohol  in  felted  needles. 
M.P.  134°.  It  is  soluble  in  alcohol,  ether,  benzene,  xylene,  and  chloro- 
form. It  has  a  peculiar  odor.  It  sublimes  undecomposed.  Cyanogen 
chloride  does  not  react.  Chloroformic  ester  gives  no  satisfactory  re- 
sult.147 It  reacts  with  mercuric  halides  in  the  ordinary  way  forming 
2-methyl-5-isopropylphenylmercuric  halides.  The  melting  points  are: 
chloride  156°,  bromide  163°,  iodide  169°. 

Mercury  Derivatives  of  Cyclohexane. 

Mercuribis-cyclohexane. 

A  poor  yield  of  this  substance  is  obtained  by  heating  cyclohexyl 
magnesium  bromide  with  mercuric  bromide  in  ether.  It  forms  crystals 
which  are  soluble  in  hot  alcohol.  Precipitation  of  the  hot  alcoholic 
solution  by  water  gives  granules  melting  78-9°.  It  is  very  unstable, 
being  decomposed  by  light  and  heat.  It  is  more  soluble  than  mercury 
diphenyl.  It  reacts  with  alcoholic  solutions  of  mercuric  salts  even  in 
the  cold  forming  cyclohexylmercuric  halides.  Cyclohexylmercuric  com- 
pounds reduce  silver  and  gold  solutions  in  the  presence  of  acid  but 
have  little  effect  on  ammoniacal  silver  solution  or  Fehling's  solution.148 

Cyclohexylmercuric  chloride. 

Cyclohexyl  magnesium  chloride  is  treated  with  an  excess  of  mer- 
curic chloride.  Another  preparation  is  by  the  action  of  mercuric  chlo- 
ride on  mercuribis-cyclohexane.  It  forms  white  leaflets  when  crystal- 
lized from  benzene  or  alcohol.  M.P.  164°  (CClHg). 

Cyclohexylmercuric  bromide. 

It  is  prepared  like  the  chloride  from  the  Grignard  reagent.  It 
forms  white  leaflets  from  benzene.  (CBrHg).  M.P.  153°.  10  gm.  of 
benzene  at  29°  dissolves  .3330  gm.  of  the  substance  while  10  gm.  of 
absolute  alcohol  at  the  same  temperature  dissolves  only  0.0424  gm. 
It  is  insoluble  in  water,  difficultly  soluble  in  cold  alcohol  and  low 
boiling  ligroin,  more  soluble  in  ether  and  benzene  especially  on  heat- 
ing, very  soluble  in  pyridine,  aniline,  and  dimethylaniline  even  cold. 
It  is  sensitive  to  light. 

'«  Michaelis,  Ber.  28  (1895),  592.     Paterno  and  Colombo,  B&r.  10   (1877),  1749. 
»8  Griittner,  Ber.  47  (1914),  1655. 


DERIVED  FROM  AROMATIC  NITRO  COMPOUNDS    189 

Cyclohexylmercuric  iodide. 

The  corresponding  bromide  is  dissolved  in  alcohol  and  benzene  and 
refluxed  with  potassium  iodide.  It  is  recrystallized  from  benzene  or 
alcohol.  (CIHg).  It  forms  white  leaflets  which  are  sensitive  to  light. 
M.P.  143°.  If  heated  to  159°  it  decomposes  giving  bubbles  and  mer- 
curic iodide. 

A  peculiar  method  of  preparing  the  iodide  is  by  the  treatment  of 
cyclohexyl  iodide  with  sodium  amalgam  which  would  be  expected  to 
give  mercuribis-cyclohexane.149 

Cyclohexylmercuric  cyanide. 

An  ether  solution  of  mercuribis-cyclohexane  is  treated  with  an  alco- 
holic solution  of  mercuric  cyanide  and  evaported  to  dryness.  The  resi- 
due is  crystallized  from  alcohol.  (CHNHg).  It  forms  white  leaflets 
sensitive  to  light.  M.P.  144°.  It  decomposes  at  190°  giving  mercury. 
It  is  more  soluble  than  the  corresponding  halides. 

Cyclohexylmercuric  sulfide. 

A  solution  of  the  bromide  in  pyridine  and  dry  ether  is  treated  with 
hydrogen  sulfide  at  -10°.  A  pure  white  precipitate  is  obtained  which 
is  fairly  soluble  in  pyridine  and  ammonium  sulfide.  (SHg).  It  is  in- 
soluble in  common  solvents.  When  wet  it  is  unstable,  turning  black 
in  a  few  hours.  Kept  dry  and  dark  in  a  vacuum  it  is  stable  for  several 
days.  It  decomposes  on  heating  without  melting. 

Mercury  Derivatives  of  Aromatic  Nitro  Compounds. 

o-Nitrophenylmercuric  Chloride.150 

Mercuric  acetate  is  heated  with  five  times  its  weight  of  nitrobenzene 
in  an  oil  bath  at  150°  until  it  is  all  dissolved.  The  heating  is  continued 
until  a  sample  gives  no  mercuric  oxide  when  tested  with  sodium  hy- 
droxide. On  cooling  a  small  amount  of  a  white  crystalline  substance 
separates.  This  gives  the  reactions  of  a  mercurous  compound  but  is 
not  mercurous  acetate.  The  filtrate  from  these  crystals  is  treated  with 
an  excess  of  sodium  chloride  solution  and  steam  distilled  to  remove 
the  excess  of  nitrobenzene.  The  residue  is  dried,  powdered,  and  ex- 
tracted with  100-120°  ligroin.  Almost  all  of  the  solid  dissolves. 
On  cooling,-  fine  slightly  yellow  crystals  are  obtained.  These  are  re- 

149  KurssanoT,  Chftn,  Zentr.  1899  II  477. 
««Dimroth,  Ber.  35   (1902),  2036. 


190  COMPOUNDS  OF  MERCURY 

crystallized  from  glacial  acetic  acid.  M.P.  182°.  It  is  insoluble  in 
water  and  most  organic  solvents  but  is  soluble  in  ether  and  in  high 
boiling  ligroin.  When  treated  with  bromine  it  gives  o-bromonitro- 
benzene. 

o-Nitrophenylmercuric  chloride  does  not  react  with  arsenic  tri- 
chloride either  on  the  water  bath  or  at  200°. 151 

This  substance  has  also  been  made  by  the  method  of  Peters  from 
o-nitrobenzene  sulfmic  acid  and  mercuric  chloride  in  aqueous  alco- 
hol.151a  The  reaction  is  complete  in  45  minutes.  The  precipitate  is 
extracted  with  hot  acetone.  The  extract  is  evaporated  to  dryness  and 
the  residue  is  crystallized  from  alcohol.  It  forms  faintly  yellow 
crystals  which  melt  at  185°  (corr.).  Yield  78  per  cent.  (N).  It  is 
very  soluble  in  acetone,  soluble  in  hot  alcohol,  very  little  soluble  cold. 
It  does  not  react  with  ammonium  sulfide.  Boiling  hydrochloric  acid 
gives  nitrobenzene.  Bromine  in  potassium  bromide  solution  gives 
o-bromonitrobenzene.  Boiling  for  hours  with  an  excess  of  5  per  cent 
sodium  hydroxide  gives  no  action. 

The  identity  of  the  compounds  obtained  directly  from  nitrobenzene 
and  from  o-nitrobenzene  sulfinic  acid  prove  that  the  direct  mercura- 
tion  of  nitrobenzene  introduces  the  mercuri  group  in  the  ortho  po- 
sition. 

m-Nitropheny  Inter  curie  Chloride  .152 

m-Nitrobenzene  sulfinic  acid  and  mercuric  chloride  are  boiled  in 
aqueous  alcohol  for  20  hours.  The  product  is  isolated  in  the  same 
way  as  the  ortho  compound.  Yield  42  per  cent.  M.P.  236-7^  (corr.) 
(NHg).  It  is  less  soluble  than  the  ortho  compound.  It  reacts  less 
readily  with  hydrochloric  acid  than  the  ortho  and  para  compounds. 
Bromine  converts  it  to  m-bromonitrobenzene. 

p-Nitrophenylmercuric  Chloride.153 

It  is  prepared  from  the  sulfinic  acid  in  the  same  way  as  the  ortho 
and  meta  compounds.  It  separates  from  alcohol  in  colorless  needles 
which  melt  with  decomposition  at  265-6°  (corr.)  (N).  Its  properties 
and  solubilities  resemble  those  of  the  ortho  compound.  Bromine  trans- 
forms it  to  p-bromonitrobenzene. 

151  Roeder  and  Blasi,  Ber.  47    (1914),  2752. 

151*  Kharasch  and  Chalkley,  J.  Am.  Chem.  Soc.  43   (1921),  611. 

152  IU&. 
188  IMd. 


DERIVED  FROM  AROMATIC  NITRO  COMPOUNDS    191 

Mercuribis-2,  4,  6-trinitrobenzene.15* 

The  mercuric  salt  of  trinitrobenzoic  acid  on  heating  loses  two 
molecules  of  carbon  dioxide  and  forms  the  mercury  diphenyl  deriva- 
tive. 

As  would  be  expected,  the  bromonitrobenzenes  do  not  give  organic 
mercury  compounds  when  treated  with  sodium  amalgam.155 

The  nitrotoluenes  react  with  hot  sodium  hydroxide  and  mercuric 
oxide  to  form  compounds  in  which  the  mercury  enters  the  methyl 
group.  The  ortho  compound  gives  mainly  a  disubstituted  product  con- 

Hg 
/      \ 

taining  the  grouping  —  CH  0.    A  smaller  amount  of  a  mono- 

\       / 
Hg 

substituted  product  is  obtained  having  the  grouping  —  CH2  —  HgOH. 
The  para  compound  and  the  dinitro  compound  give  mixtures  which 
are  hard  to  separate.156 

Anhydride  of  o-nitrobenzal  dimercuric  hydroxide, 

Hg 

/      \ 

N02  —  C6H4  —  CH  0. 

\      / 

Hg 

Preparation. 

Mercuric  oxide,  prepared  from  cold  mercuric  chloride  solution  and 
cold  sodium  hydroxide,  is  well  washed  and  mixed  with  dilute  sodium 
hydroxide  solution.  The  mixture  is  heated  to  boiling  under  a  reflux 
condenser.  It  is  stirred  by  a  current  of  air.  The  o-nitrotoluene  is 
added  gradually  in  small  amounts.  The  mixture  is  boiled  for  one  and 
a  half  hours  and  then  cooled.  The  precipitate  is  filtered  off  and  dried. 
Yield  96  per  cent.  (CHNHg) .  The  mother  liquor  treated  with  dilute 
hydrochloric  acid  gives  a  precipitate  of  the  impure  monosubstituted 
compound,  N02  —  C6H4  —  CH2  —  HgCl. 

Properties. 

The  anhydride  forms  an  intensely  yellow  solid.  It  is  insoluble  in 
common  solvents  but  is  fairly  soluble  in  acetic  acid  and  less  so  in  20 

154  private  communication,  M.  S.  Kharascn. 
155Dreher  and  Otto,  Ann.  154  (1870),  125. 
"•Reissert,  Ber.  40  (1907),  4209. 


192  COMPOUNDS  OF  MERCURY 

per  cent  sulfuric  acid.    It  is  soluble,  even  in  the  cold,  in  sodium  bi- 
sulfite solution.    This  solution  decomposes  on  standing. 

The  best  method  of  purifying  the  anhydride  is  to  dissolve  it  in  a 
large  volume  of  hot  20  per  cent  acetic  acid.  On  cooling  and  diluting, 
a  slight  precipitate  forms.  This  is  filtered  off  and  the  filtrate  is 
treated  with  sodium  hydroxide.  At  first,  a  light  yellow  precipitate 
of  the  acetate  forms.  On  standing  in  contact  with  an  excess  of  base 
this  takes  on  the  darker  hue  of  the  anhydride.  The  final  product  con- 
sists of  deep  yellow  crystals  which  can  be  dried  on  the  water  bath 
without  decomposition.  It  darkens  and  decomposes  above  220°. 

Reactions. 

1.  With  acids. 

The  anhydride  treated  with  hydrochloric  acid  of  over  30  per  cent 
is  split,  giving  inorganic  mercury  and  anthranil.  This  change  makes 
possible  a  very  interesting  intramolecular  oxidation  and  reduction.  It 
is  possible  to  go  from  o-nitrotoluene  to  the  mercury  compound,  then 
to  anthranil,  and  finally  to  anthranilic  acid  without  the  use  of  any 
oxidizing  or  reducing  agent. 

When  the  anhydride  is  rubbed  with  10  per  cent  hydrochloric  acid 
it  is  changed  to  o-nitrobenzal  dimercuric  chloride, 

N02  — C6H4  — CH(HgCl)2.    (NC1H). 

Treatment  with  sodium  nitrite  and  sulfuric  acid  changes  the  an- 
hydride to  a  dinitrite  which  reacts  with  20  per  cent  hydrochloric  acid 
giving  o-nitrobenzaldehyde  and  an  equal  amount  of  its  oxime.  Total 
yield  73  per  cent. 

The  anhydride  treated  with  nitric  acid  gives  o-nitrobenzaldehyde  in 
87  per  cent  yield  and  about  10  per  cent  of  another  product  which  is 
possibly  o,  o'  -dinitrotolane. 

2.  With  halogens. 

Treatment  of  the  anhydride  with  the  free  halogens  gives  the  three 
o-nitrobenzal  halides. 

3.  With  reducing  agents. 

Zinc  dust  and  sulfuric  acid  reduce  the  anhydride  to  o-toluidine. 

4.  With  sulfides. 

A  suspension  of  the  anhydride  treated  with  hydrogen  sulfide  for 
five  hours  changes  only  partially  to  o-nitrotoluene  and  mercuric  sul- 
fide. About  80  per  cent  of  the  material  remains  unchanged. 


DERIVED  FROM  AROMATIC  NITRO  COMPOUNDS    193 

Besides  the  dichloride  and  the  dinitrite  mentioned  above  a  basic 
chloride  and  a  basic  sulfate  have  been  prepared  from  the  anhydride. 
A  normal  nitrate  and  sulfate  have  also  been  prepared. 

o-Nitrobenzylmercuric  chloride,  N02  —  C6H4  —  CH2  —  HgCl. 

If  the  mother  liquors  from  the  disubstituted  compound  are  treated 
with  an  excess  of  dilute  hydrochloric  acid  a  small  amount  of  the  mono- 
substituted  compound  is  precipitated.  This  can  be  purified  by  treat- 
ing with  sodium  hydroxide,  filtering,  and  acidifying  with  hydrochloric 
acid  and  then  repeating  the  process,  using  ammonium  hydroxide 
instead  of  sodium  hydroxide.  This  process  gives  colorless  crystals. 
(CHNClHg).  M.P.  145-6°.  It  is  easily  soluble  in  acetone  and  ben- 
zene, less  soluble  in  alcohol,  rather  difficultly  in  ether,  and  very  little 
in  water.  It  is  soluble  in  bases. 

p-Nitrotoluene  treated  with  sodium  hydroxide  and  mercuric  oxide 
gives  no  alkali  soluble  product.  The  insoluble  product  obtained  con- 
tains more  than  two  atoms  of  mercury.  An  excess  of  dilute  nitric  acid 
gives  p-nitrobenzoic  acid  indicating  that  the  mercuration  takes  place 
in  the  side  chain. 

2,  4-Dinitrotoluene  reacts  very  readily  with  mercuric  oxide  and 
sodium  hydroxide  or  sodium  ethylate.  The  products  are  hard  to  purify. 
They  react  more  readily  with  sulfides  than  do  the  mercury  compounds 
of  o-nitrotoluene.  Treatment  with  nitric  acid  of  Sp.  g.  1.4  gives  2,  4-di- 
nitrobenzoic  acid. 

Mercury  di-(2,  4-dinitrobenzyl)  .15T 

The  mercuric  salt  of  2,  4-dinitrophenyl  acetic  acid  is  heated  to 
eliminate  two  molecules  of  carbon  dioxide.  If  the  product  is  heated 
still  hotter  it  loses  metallic  mercury  and  forms  tetranitrodibenzyl.  This 
loss  of  mercury  takes  place  more  rapidly  in  the  presence  of  pyridine. 

Mercury  Derivatives  of  Sulfinic  and  Sulfonic  Acids. 

Benzene  sulfinic  acid  and  p-toluene  sulfinic  acid  react  with  mercuric 
chloride  at  0°  to  form  mercuric  salts  of  the  acids.  If  heated  with 
alcoholic  mercuric  chloride  the  sulfinic  acids  give  sulfur  dioxide,  hydro- 
chloric acid;  and  the  corresponding  arylmercuric  chloride.  There  is 
also  some  reduction  of  the  mercuric  chloride  to  calomel.  If  the  ace- 

187  Private  communication,  M.  S.  Kharascn. 


194  COMPOUNDS  OF  MERCURY 

tate  or  nitrate  is  used  instead  of  mercuric  chloride  much  metallic 
mercury  is  formed.158 

This  method  has  recently  been  applied  in  the  preparation  of  the 
three  nitrophenylmercuric  chlorides  from  the  corresponding  nitrosul- 
finic  acids.159  It  has  also  been  applied  in  the  preparation  of  beta- 
naphthylmercuric  chloride.160 

Benzene  suljonic  acid  can  be  mercurated  by  heating  with  mercuric 
oxide  until  the  solution  gives  no  action  with  sodium  hydroxide.  The 
product  has  not  been  obtained  pure.  Treatment  of  the  impure  sub- 
stance with  bromine  gives  m-bromobenzoic  acid  and  some  dibromo- 
benzoic  acid.  These  results  indicate  that  the  mercury  enters  the  nu- 
cleus in  the  meta  position  to  the  sulfonic  acid  group.  If  this  is  true 
the  case  is  of  great  interest  as  being  the  only  one  in  which  mercury 
takes  a  position  meta  to  the  orienting  group.  The  mercuration  of 
benzoic  acid  and  nitrobenzene  give  ortho  compounds.161 

Mercury  Derivatives  of  Phenylacetyiene. 

Phenylacetylene  when  treated  with  mercuric  salts  gives  products 
which  on  acidification  yield  acetophenone.  This  reaction  resembles 
that  of  acetylene  which  gives  acetaldehyde.  In  each  case  the  net  re- 
sult is  the  addition  of  water  to  the  triple  bond.  As  in  the  case  of  acety- 
lene, there  is  no  agreement  as  to  the  mechanism  of  the  reaction.  Man- 
chot 162  believes  that  the  mercury  compound  is  a  complex  molecular 
compound  of  mercuric  phenyl  acetylide  and  mercuric  salts  while 
Biltz 163  regards  this  compound  as  acetophenone  mercurated  in  the 
methyl  group.  The  former  believes  that  acidification  simply  liberates 
phenylacetylene  which  is  then  hydrated  more  rapidly  in  the  presence 
of  the  mercuric  salts  which  are  formed  in  the  reaction.  The  latter 
believes  that  the  mercurated  acetophenone  gives  the  usual  reaction  of 
organic  mercury  compounds  with  acids,  namely,  the  replacement  of 
mercury  by  hydrogen.  Manchot  strengthens  his  argument  by  showing 
that  the  triple  bond  can  be  hydrated  by  acid  alone.  Thus  phenyl 
acetylene  gives  a  small  amount  of  acetophenone  when  heated  with 

168  Peters,  Ber.  38  (1905),  2567. 

189  Kharasc'h  and  Chalkley,  J.  Am,  Chem.  Soc.  43   (1921),  611. 
160  Unpublished  results,  Whltmore  and  L.  F.  Howe. 

>61  Reissert,  loc.  cit.     Dimroth,  Chem.  Zentr.  1901   I   450.     Rother,  Dissert.  Berlin 
1911,  p.  8. 

162  Manchot  and  Haas,  Ann.  399   (1913),  123. 
1153  Biltz  and  Keinkober,  Ann.  404    (1914),  219. 


DERIVED  FROM  AROMATIC  HYDROCARBONS       195 

dilute  hydrochloric  acid.  Piperonylacetylene  boiled  with  hydrochloric 
acid  even  for  a  few  minutes  is  changed  completely  to  the  ketone.164 

Phenyl  acetylene  treated  with  mercuric  chloride  gives  an  oil  unless 
an  excess  of  the  mercuric  salt  is  used.  In  that  case  crystals  are  ob- 
tained. These  crystals  give  analyses  for  C16H11Hg5Cl502  or 
C16H13Hg5Cl503.  Manchot  gives  molecular  formulas  corresponding 
to  these  empirical  formulas:— 

I.     (C6H5C  E=C)2Hg.2HgCl2.HgO.Hg(OH)Cl. 
II.     (C6H5C  =  CH)  2.2HgCl2.2HgO.Hg  (OH)  Cl. 

The  first  seems  more  probable.  When  two  molecules  of  phenyl  acety- 
lene react  with  an  excess  of  mercuric  chloride  almost  exactly  5  mole- 
cules of  hydrochloric  acid  are  split  out  as  can  be  shown  by  titrating 
the  filtrate  from  the  mercury  compound.  The  formation  of  the  com- 
pound C6H5  —  CO  —  C(HgCl)3  would  require  the  formation  of  6 
molecules  of  hydrochloric  acid  instead  of  5.  Biltz  believes  that  Man- 
chot's  result  of  about  5  molecules  of  hydrochloric  acid  can  be  explained 
in  the  following  ways: 

1.  The  experimental  difference  is  not  great. 

2.  The  product  may  contain  some  dimercurated  product  the  for- 
mation of  which  would  give  a  smaller  amount  of  acid. 

3.  Some  of  the  phenyl  acetylene  may  have  remained  unchanged. 
It  would  be  more  logical  to  do  the  calculations  from  the  amount  of 
precipitate  actually  formed  than  from  the  amount  of  material  exposed 
to  the  reaction.165 

Mercuric  phenylacetylide 166  reacts  with  mercuric  chloride  and  a  lit- 
tle hydrochloric  acid  giving  the  same  product  as  phenyl  acetylene  itself. 
This  method  of  preparation  throws  no  light  on  the  nature  of  the  product 
as  the  acid  used  may  liberate  phenyl  acetylene  which  then  reacts  with 
the  mercuric  salt. 

Properties  of  the  product  from  phenyl  acetylene  and  mercuric  chloride. 
It  forms  a  white  amorphous  solid  insoluble  in  all  common  solvents. 
It  gives  no  reaction  with  bases.  Ammonium  sulfide  blackens  it  at  once 
with  the  formation  of  mercuric  sulfide.  Four  samples  of  the  substance 
made  with  amounts  of  mercuric  chloride  varying  from  1.8  to  3  mole- 
cules give  analyses  as  follows:  6  analyses  for  carbon,  13.28  to  13.78; 

384  Manchot  and  Haas,  loc.  cit. 
168  Biltz  and  Reinkober,  loc.  cit. 
1MNef,  Ann.  308  (1899),  299. 


196  COMPOUNDS  OF  MERCURY 

6  for  hydrogen,  .91  to  1.42;  11   for  mercury,  69.72  to  72.39;  2  for 
chlorine,  12.91  and  12.97. 

Reactions. 

1.  Action  with  hydrochloric  acid. 

If  the  precipitate  is  refluxed  with  dilute  hydrochloric  acid  and  not 
steam  distilled  for  several  hours  the  only  product  is  acetophenone. 
The  precipitate  from  8  gm.  of  phenyl  acetylene  gives  6.4  gm.  of  aceto- 
phenone and  no  phenyl  acetylene.  However,  if  the  mixture  is  steam 
distilled  as  soon  as  the  acid  is  added  a  little  phenyl  acetylene  is  formed. 
In  this  way  35  gm.  of  the  precipitate  yields  .9  gm.  of  phenyl  acetylene 
boiling  over  a  range  of  27  degrees  and  4.1  gm.  of  acetophenone  boiling 
over  a  range  of  5  degrees.  If  all  of  the  precipitate  were  changed  to 
phenylacetylene  it  would  give  5.  gm.  If  acetophenone  were  the  only 
product  the  yield  would  be  5.9  gm. 

2.  Action  with  bromine. 

The  precipitate  suspended  in  chloroform  reacts  with  four  atoms 
of  bromine  for  every  triple  bond  originally  present.  No  hydrobromic 
acid  is  formed.  If  more  bromine  is  added  it  acts  more  slowly  and 
hydrobromic  acid  escapes.  The  organic  products  of  these  reactions 
have  not  been  studied.  Manchot  suggests  that  the  reaction  with  four 
atoms  of  bromine  gives  mercuric  bromide  and  phenylacetylene  di- 
bromide.  A  more  natural  product  would  appear  to  be  tribromostyrene, 
C6H5  —  CBr  =  CBr2.  If  Biltz  is  right  in  assuming  that  the  precipi- 
tate is  a  mixture  of  di-  and  tri-mercurated  acetophenones  the  product 
of  bromination  should  be  a  mixture  of  di-  and  tribromacetophenones. 
A  careful  study  of  the  organic  product  of  the  bromination  might  well 
throw  light  on  the  true  nature  of  the  original  precipitate. 

Product  of  the  action  of  phenyl  acetylene  with  mercuric  bromide.167 
Phenyl  acetylene  treated  with  3  molecules  of  mercuric  bromide  in 
a  large  volume  of  water  yields  a  crystalline  yellowish  precipitate. 
This  is  insoluble  in  water  and  only  very  slightly  soluble  in  organic  sol- 
vents.   Long  extraction  with  solvents  produces  no  change  in  the  compo- 
sition.    The  analyses  for  carbon,  hydrogen,  mercury,   and  bromine 
agree  fairly  well  with  the  formulas  C16H10Hg4Br40  and  C8H6Hg2Br20. 
Manchot  uses  the  following  molecular  formulas: 
I.     (C6H5C  =  C)2Hg.2HgBr2.HgO. 
II.    C6H5C  =  CH.HgBr2.HgO. 

167  Manchot  an<}  Haas,  loc,  cit.  144. 


DERIVED  FROM  AROMATIC  HYDROCARBONS        197 

Again  the  first  formula  is  the  more  likely.  The  substance  does  not  re- 
act with  bases  even  on  heating.  With  ammonium  sulfide  it  gives 
mercuric  sulfide  at  once. 

Reactions. 

1.  With  hydrochloric  acid. 

Refluxing  with  dilute  acid  gives  no  change.  Concentrated  hydro- 
chloric acid  gives  an  oil.  If  this  is  steam  distilled  at  once  it  yields 
1.9  gm.  of  phenylacetylene  boiling  over  a  range  of  7  degrees  and  1.4 
gm.  of  acetophenone  of  M.P.  17-18°.  The  theoretical  yield  would  be 
5.3  gm.  or  6.3  gm.  respectively. 

2.  With  bromine. 

As  in  the  case  of  the  compound  from  mercuric  chloride  4  bromine 
atoms  react  for  every  triple  bond  used.  The  organic  product  has  not 
been  studied. 

Mercuric  phenylacetylide,  (C6H5  —  C  =  C)2Hg. 168 

Phenylacetylene  and  mercuric  oxide  give  a  product  which  can  be  re- 
crystallized  from  hot  alcohol  in  white  leaflets.  Treatment  with  mer- 
curic chloride  and  a  little  hydrochloric  acid  gives  the  same  product  as 
phenyl  acetylene  itself.  It  is  easily  soluble  in  ether.  Manchot  ex- 
tracted the  precipitates  obtained  from  phenyl  acetylene  and  mer- 
curic salts  with  ether  but  was  unable  to  remove  any  of  the  acetylide 
assumed  to  be  present  in  the  "molecular"  compounds.  He  concluded 
that  the  acetylide  must  be  "chemically  combined"  in  the  compounds. 

Mercury  Derivatives  of  Naphthalene. 

a-Mercury  Dinaphthyl. 
Preparation. 

Alpha  bromonaphthalene  heated  with  xylene  and  pasty  sodium 
amalgam  for  18  hours  on  an  oil  bath  gives  small  yellowish  crystals 
of  the  mercury  compound.169  A  better  yield  is  obtained  if  benzene  is 
used  as  the  solvent  and  one-tenth  volume  of  ethyl  acetate  is  added.170 
Four  per  cent  sodium  amalgam  is  recommended.171 

168Nef,,loc.  cit. 

169  Otto  and  Mories,  Ann.  147   (1868),  167. 

170  Otto,  Ann.  154  (1870),  188. 
"'Michaelis,  Ber.  27   (1894),  249. 


198  COMPOUNDS  OF  MERCURY, 

Properties. 

Alpha  mercury  dinaphthyl  forms  small  white  shiny  rhombic  prisms. 
It  is  odorless  and  is  unchanged  by  air  or  light.  It  is  insoluble  in  water, 
slightly  soluble  in  boiling  alcohol,  cold  benzene,  and  ether,  easily 
soluble  in  hot  carbon  disulfide  and  chloroform,  less  easily  soluble  in 
boiling  benzene.  Alcohol  or  ether  will  precipitate  it  from  its  solution 
in  carbon  disulfide.  It  is  best  crystallized  from  hot  benzene,  carbon 
disulfide,  or  amyl  alcohol.  (CHHg).  M.P.  243°.  On  heating  to  a 
higher  temperature  it  gives  carbon,  mercury,  and  a  brown  oil  which 
crystallizes  on  cooling.  The  density  of  alpha  mercury  dinaphthyl  is 
about  1.9.172 

Reactions. 

1.  Heating. 

When  mercury  dinaphthyl  is  heated  with  soda  lime  the  products 
are  mercury,  naphthalene,  and  a  substance  melting  at  133°  which  may 
be  impure cux'-dinaphthyl  (M.P.  154° ).173 

2.  With  metals. 

A  solution  in  carbon  disulfide  does  not  react  with  zinc,  copper,  or 
tin  in  the  cold.  No  experiments  at  higher  temperatures  have  been 
tried. 

3.  With  halogens. 

Iodine  in  carbon  disulfide  gives  a  compound  which  was  at  first 
thought  to  be  (C10H7)2HgI2  but  has  since  been  found  to  be  alpha 
naphthylmercuric  iodide.  An  excess  of  iodine  gives  mercuric  iodide. 
The  other  product  in  these  reactions  is  a-iodonaphthalene  which  was 
first  made  by  this  process.  Bromine  acts  like  iodine. 

4.  With  acids. 

Hydrochloric  acid  gives  mercuric  chloride  and  naphthalene.  No 
mention  is  made  of  any  intermediate  formation  of  naphthylmercuric 
chloride.  Formic  acid  gives  naphthylmercuric  formate  and  naphtha- 
lene. Similar  reactions  are  obtained  with  acetic  and  butyric  acids. 
Fuming  nitric  acid  acts  violently  even  in  the  cold  giving  mercuric 
nitrate  and  nitro  derivatives  of  naphthalene.  Dilute  nitric  acid  gives 
some  unnitrated  naphthalene.  Concentrated  sulfuric  acid  gives  mer- 
curic sulfate  and  naphthalene  sulfonic  acid.  15  per  cent  hydrocyanic 

"'Schroder,  Ber.  12   (1879),  564. 
173  Otto  and  Mories,  loc.  cit. 


DERIVED  FROM  AROMATIC  HYDROCARBONS       199 

acid  gives  no  action  even  on  heating.    The  filtrate  contains  no  mer- 
curic ions.174  • 

5.  With  arsenic  trichloride.175 

The  products  of  the  reaction  at  a  high  temperature  are  mercuric 
chloride  and  a-naphthyl  dichlorarsine. 

6.  With  thionyl  chloride. 

A  stormy  reaction  results  when  thionyl  chloride  is  added  to  a-mer- 
cury  dinaphthyl.  The  mixture  must  be  cooled.  When' water  is  added 
an  oil  separates.  When  this  is  washed  with  water  and  ether  it  solidi- 
fies. The  solid  can  be  distilled,  most  of  it  boiling  at  256°.  The  dis- 
tillate solidifies  and  can  be  recrystallized  from  alcohol,  M.P.  60°  cor- 
responding to  beta  chloronaphthalene.  Apparently  this  change  of  an 
alpha  to  a  beta  derivative  of  naphthalene  has  not  been  questioned  or 
studied  farther.176 

7.  With  mercuric  salts. 

Mercuric  chloride  in  acetone  reacts  readily  to  form  a-naphthyl- 
mercuric  chloride.177  1  gm.  of  a-mercury  dinaphthyl  is  added  to  50  c.c. 
of  hot  acetone  which  is  insufficient  to  dissolve  it.  When  .6  gm.  of 
mercuric  chloride  is  added  all  goes  into  solution.  Cooling  causes  the 
separation  of  1.4  gm.  of  a-naphthylmercuric  chloride.  The  same  re- 
action carried  out  in  carbon  disulfide  solution  appears  to  give  entirely 
different  results.  Mercury  dinaphthyl  warmed  a  long  time  with  mer- 
curic chloride  in  carbon  disulfide  and  then  evaporated,  leaves  a  resi- 
due from  which  water  extracts  mercuric  chloride  leaving  unchanged 
mercury  dinaphthyl.178  Mercury  dinaphthyl  heated  one  hour  with 
mercuric  iodide  and  alcohol  at  150°  gives  a-naphthylmercuric  iodide.179 

8.  With  oxides  of  nitrogen. 

Nitrogen  trioxide  in  chloroform  at  0°  gives  a-naphthyl  diazonium 
nitrate  and  a  solution  of  a-naphthylmercuric  nitrate.  This  cannot 
be  isolated  but  gives  a  precipitate  of  the  chloride  when  treated  with 
dilute  hydrochloric  acid.  Nitrogen  textroxide  in  chloroform  at  0° 
gives  a  bright  yellow  crystalline  precipitate  which  is  soluble  in  alco- 
hol. If  treated  with  dilute  hydrochloric  acid  it  gives  a-naphthyl  mer- 

"*Otto  and  Mories,  loc.  cit. 

"'Kelbe,  Ber.  11   (1878),  1503.     Michaelis  and  Schulte,  Ber.  15   (1882),  1954. 

""Heumann  and  Kochlin,  Ber.  16   (1883),  1627. 

"TSteinkopf,  Ann.  413   (1917),  313,  330. 

178  Otto  and  Mories,  loc.  cit. 

"9Otto,  Ann.  154  (1870),  190. 


200  COMPOUNDS  OF  MERCURY 

curie  chloride.    The  filtrate  from  the  original  precipitate  gives  naph- 
thalene.   No  diazonium  nitrate  or  nitroso  compound  is  formed.180 
9.    Miscellaneous. 

An  alcohol  solution  of  a-mercury  dinaphthyl  does  not  react  with 
hydrogen  sulfide.  Sodium  amalgam  and  alcohol  give  no  action  on 
the  mercury  compound.  Ethyl  iodide  gives  no  action. 

a-Naphthylmer  curie  chloride. 
Preparation. 

1.  From  mercury  dinaphthyl  and  mercuric  chloride  in  alcohol  or 
acetone. 

2.  From  the  nitrate  and  dilute  hydrochloric  acid. 

Properties. 

It  forms  silky  quadratic  tablets.  It  is  insoluble  in  water,  difficultly 
soluble  in  hot  alcohol,  more  soluble  in  hot  benzene.  M.P.  188-9°.  It 
reacts  with  sodium  iodide  in  acetone  giving  a-naphthylmercuric  iodide 
but  no  mercury  dinaphthyl.181 

a-Naphthylmer  curie  bromide. 
Preparation. 

1.  From  mercury  dinaphthyl  and  bromine. 

2.  From  mercury  dinaphthyl  heated  with  mercuric  bromide  and 
alcohol  one  hour  at  120°. 

3.  From   naphthyl   magnesium   bromide    and   mercuric   bromide 
heated.182 

Properties. 

The  bromide  forms  shiny  pointed  leaflets.  M.P.  202°.  It  is  very 
soluble  in  aniline  from  which  it  separates  in  well  formed  crystals.  It 
can  also  be  recrystallized  from  pyridine.  It  is  insoluble  in  water, 
soluble  in  hot  alcohol,  chloroform,  benzene,  and  carbon  disulfide. 

Reactions. 

An  excess  of  ethyl  magnesium  bromide  gives  mercury  diethyl.183 
An  excess  of  a-naphthyl  magnesium  bromide  gives  only  a  small  yield 
of  a-mercury  dinaphthyl.184 

18«Kunz,  Ber.  31   (1898),  1531. 

181  Steinkopf ,  loc.  cit. 

182Hilpert  and  Griittner,  Ber.  46   (1913),  1686. 

183  Hilpert  and  Griittner,  Ber.  48   (1915),  908. 

184Hilpert  and  Gruttner,  Ber.  46  (1913),  1686. 


DERIVED  FROM  AROMATIC  HYDROCARBONS       201 

a-Naphthylmer  curie  iodide. 

Mercury  dinaphthyl  is  treated  with  iodine  in  carbon  disulfide  or  is 
heated  with  mercuric  iodide  and  alcohol  at  150°.  The  iodide  is  in- 
soluble in  ether  and  water,  soluble  in  hot  alcohol,  chloroform,  benzene, 
and  carbon  disulfide.  It  is  best  crystallized  from  a  large  volume  of 
boiling  alcohol  or  a  mixture  of  alcohol  and  benzene.  (I).  M.P.  185°. 
It  reacts  with  sodium  amalgam  in  alcohol  or  benzene  giving  a-mercury 
dinaphthyl.185 

a-Naphthylmer  curie  formate. 

Mercury  dinaphthyl  is  treated  with  formic  acid  and  the  resulting 
solution  is  poured  into  water.  The  formate  is  an  oil.186 

a-Naphthylmer  curie  acetate. 
Preparation  and  Properties. 

Mercury  dinaphthyl  is  dissolved  in  glacial  acetic  acid  and  the  solu- 
tion is  diluted  with  water.  The  naphthalene  is  filtered  off  and  the  fil- 
trate is  evaporated  to  obtain  the  acetate.  The  acetate  is  easily  solu- 
ble in  hot  alcohol  from  which  it  separates  in  fine  needles  on  cooling.  It 
is  almost  insoluble  in  water,  slightly  soluble  in  ether,  easily  soluble  in 
hot  acetic  acid,  alcohol,  carbon  disulfide,  benzene,  and  chloroform.  It 
is  soluble  in  fats.187  M.P.  154°. 

Reactions. 

1.  Heating  above  the  melting  point  gives  carbon  and  an  oily  dis- 
tillate. 

2.  With  hydrochloric  acid  it  gives  naphthalene,  mercuric  chloride, 

and  acetic  acid. 

3.  With  sodium  amalgam. 

In  alcohol  the  reaction  gives  naphthalene,  sodium  acetate,  and  me- 
tallic mercury.  This  is  in  distinct  contrast  to  the  action  of  the  iodide 
which  gives  a-mercury  dinaphthyl  when  treated  with  sodium  amalgam 
even  in  alcohol. 

4.  With  sulfides. 

An  alcoholic  solution  reacts  with  hydrogen  sulfide  giving  a  white 
cheesy  precipitate  which  is  insoluble  in  common  solvents  except  ben- 
zene which  dissolves  it  slightly.  Heating  with  an  excess  of  ammonium 

185  Otto,  Ann.  154  (1870),  190. 


1MFraenkel,  Arzneimittelsynthese,  4th  Ed.  1919,  671. 


202  COMPOUNDS  OF  MERCURY 

sulfide  at  100°  gives  naphthalene,  ammonium  acetate,  and  mercuric 

sulfide. 

5.    With  halogens. 

Iodine  gives  mercuric  iodide,  acetic  acid,  and  naphthyl  iodide. 

a-Naphthylmercuric  butyrate. 

Mercury  dinaphthyl  is  treated  with  butyric  acid.  The  product 
consists  of  fine  silky  rhombic  needles.  M.P.  200°.  It  is  hardly  soluble 
in  cold  water,  readily  soluble  in  hot  water,  alcohol,  and  butyric  acid. 

a-Naphthylmercuric  thiocyanate. 

Mercury  dinaphthyl  and  mercuric  thiocyanate  are  heated  in  alco- 
hol at  120°.  The  product  forms  fine  white  tablets  which  are  soluble 
in  hot  alcohol  and  benzene.188 

a-Naphthylmercuric  nitrate. 

The  chloride  is  treated  with  alcoholic  silver  nitrate.  The  nitrate 
is  also  obtained  in  chloroform  solution  by  treating  mercury  dinaphthyl 
with  nitrogen  trioxide.  It  forms  fine  white  needle  crystals.  It  re- 
acts with  dilute  hydrochloric  acid  giving  the  chloride. 

a-Naphthylmercuric  sulfide. 

The  acetate  is  treated  with  ammonium  sulfide.  The  sulfide  is  a 
cheesy  white  precipitate.  It  is  slightly  soluble  in  benzene.  It  reacts 
with  an  excess  of  ammonium  sulfide  at  100°  to  form  mercuric  sulfide, 
naphthalene,  and  ammonium  acetate. 

fi-Mercury  Dinaphthyl. 
Preparation. 

(3-Bromonaphthalene  mixed  with  three  volumes  of  dry  xylene  and 
5  per  cent  ethyl  acetate  is  refluxed  for  30  hours  with  a  large  excess 
of  sodium  amalgam  which  is  just  liquid  at  room  temperature.  An  ex- 
cess of  benzene  is  added,  the  mixture  is  heated,  and  filtered  hot.  A 
white  crystalline  product  is  obtained  in  a  yield  of  about  30  per  cent. 
The  product  is  recrystallized  from  benzene.  p-Chloronaphthalene  re- 
acts with  sodium  amalgam  but  gives  a  much  poorer  yield  of  the  mer- 
cury compound.189 

Properties. 

(3-Mercury  dinaphthyl  forms  white  glistening  scales  or  flat  needles. 

188  Otto,  J.  prakt.  Chem.   (2)  1  (1870),  182. 

189  Chattaway,  J.  Chem.  Soc.  65    (1894),  878.     Michaelis,  Ber.  27   (1894),  251. 


DERIVED  FROM  AROMATIC  HYDROCARBONS        203 

M.P.  238°.  It  is  insoluble  in  ether  and  alcohol,  moderately  soluble  in 
hot  benzene  and  its  homologs,  chloroform,  ethylene  dibromide,  and 
carbon  disulfide. 

Reactions. 

1.  With  mineral  salts.    Mercuric  salts  and  naphthalene  or  sub- 
stituted naphthalenes  are  obtained. 

2.  Distillation  over  red  hot  soda  lime  gives  (3(3'-dinaphthyl  and 
other  products. 

3.  With  arsenic  trichloride.190 

The  reaction  takes  place  as  usual  giving  mercuric  chloride  and  the 
naphthyl  dichlorarsine. 

fi-Naphthylmercuric  halides. 

The  halides  have  been  prepared  from  (3-mercury  dinaphthyl.  The 
chloride  and  bromide  form  colorless  needles  while  the  iodide  forms 
slightly  yellow  leaflets.  The  chloride  is  the  most  soluble  of  the  three 
although  it  is  difficultly  soluble  in  all  organic  solvents  except  hot  amyl 
alcohol.  The  melting  points  are  as  follows:  chloride  271°,  bromide 
266°,  iodide  251°. 

p-Naphthylmercuric  chloride  can  be  more  conveniently  prepared 
by  the  method  of  Peters  from  the  sulfinic  acid  and  mercuric  chlo- 
ride.191 

fi-Naphthylmercuric  formate. 

The  mercury  dinaphthyl  is  heated  a  long  time  with  pure  formic 
acid  and  the  solution  is  precipitated  by  water.  After  drying,  the  naph- 
thalene is  removed  by  low  boiling  ligroin.  The  residue  is  crystallized 
from  alcohol.  It  forms  fairly  large  colorless  glassy  leaflets  which  turn 
gray  in  light.  It  is  easily  soluble  in  alcohol,  fairly  soluble  in  ether, 
benzene,  and  chloroform,  insoluble  in  water.  M.P.  155-8°.  The  cor- 
responding acetate  is  made  in  a  similar  way  and  has  similar  proper- 
ties. M.P.  148°. 

Mercury  Compounds  of  Naphthalene  Sulfonic  Acids.192 

When  the  sodium  salt  of  a-  or  |3-naphthalene  sulfonic  acid  is  heated 
with  mercuric  acetate  a  white  substance  is  obtained  which  reacts  with 

»»<>  Michaelis,  Ann.  320   (1902),  342. 

191  Unpublished  results,  Whitmore  and  L.  F.   Howe. 

192Brieger  and  Schulemann,  J.  prakt.  Chem.  (2)  89   (1914),  154. 


204  COMPOUNDS  OF  MERCURY 

sodium  hydroxide  like  a  mercuric  salt.  This  white  substance  is 
dissolved  in  acetic  acid  and  treated  with  sodium  hydroxide  until  the 
precipitate  barely  clears  on  shaking.  The  solution  is  evaporated  on 
the  steam  bath.  White  crystals  are  formed.  These  dissolve  readily  in 
water.  In  dilute  solution  the  new  substance  acts  like  a  mercuric  salt 
toward  sodium  hydroxide.  In  concentrated  solution  the  mercury  is 
in  some  form  which  does  not  react  with  sodium  hydroxide.  If  the 
concentrated  solution  is  heated  with  sodium  hydroxide  mercuric  oxide 
is  obtained. 

Mercury  Derivative  of  Dihydronaphthalene.193 

Dihydronaphthalene  reacts  with  mercuric  salts  in  such  a  way  that 
the  groups  — HgX  and  — OH  add  to  the  double  bond  in  the  ali- 
cyclic  ring.  It  thus  resembles  the  simpler  ethylene  derivatives. 

ac-2-Acetoxymercuri-3-hydroxy-tetrahydronaphthalene. 

An  ether  solution  of  dihydronaphthalene  is  shaken  for  24  hours 
with  an  aqueous  solution  of  mercuric  acetate.  Long  needles  separate. 
These  can  be  crystallized  from  benzene  or  ligroin.  M.P.  122°.  The 
substance  is  soluble  in  bases.  (No  analyses.)  The  corresponding 
bromide  is  obtained  by  dissolving  the  acetate  in  potassium  hydroxide, 
adding  the  calculated  amount  of  potassium  bromide,  and  saturating 
with  carbon  dioxide.  The  precipitate  is  washed  with  water  and  crystal- 
lized from  benzene.  It  forms  white  shining  crystals.  (CHHg).  M.P. 
159°.  The  iodide  is  prepared  in  the  same  way  as  the  bromide  and 
has  similar  properties.  (CH) .  It  melts  at  156°  turning  red. 

Mercury  Derivatives  of  Biphenyl.194 

Mercuribis-biphenyl,  (C6H5  —  C6H4  — )  2Hg. 

The  parabromide  is  treated  with  sodium  amalgam  in  the  usual 
way.  The  product  separates  from  hot  benzene  in  small  scales.  (CHHg) . 
M.P.  216°.  It  is  very  difficultly  soluble  in  common  solvents.  It  is 
very  stable,  not  being  changed  by  prolonged  boiling  with  concentrated 
hydrochloric  acid.  When  heated  in  sealed  tubes  with  mercuric  halides 
and  alcohol  it  gives  the  corresponding  p-biphenyl-mercuric  halides 
which  are  white  crystalline  powders  melting  above  325°. 

Dimercuribis-biphenyl,  Hg  (C6H4  —  C6HJ  2Hg. 

The  product  from  4,  4'-dibromobiphenyl  and  sodium  amalgam  may 
have  this  structure.  It  is  extremely  insoluble.  (No  analyses.) 

193  Sand  and  Genssler,  Ber.  36   (1903),  3706. 
»•*  Michaelis,  Ber.  28   (1895),  592. 


Chapter  X. 
Mercury  Compounds  of  Aromatic  Amines. 

Mercury  Compounds  of  Aniline. 

The  compounds  obtained  from  aniline  and  mercuric  salts  may  be 
divided  into  three  classes:  I  —  Substances  of  a  salt-like  nature  ob- 
tained by  the  direct  union  of  molecules  of  the  constituents.  II  —  Com- 
pounds in  which  hydrogen  of  the  amino  group  is  replaced  by  mercury. 
Ill  —  Compounds  in  which  hydrogen  of  the  nucleus  has  been  replaced 
by  mercury. 

Double  Compounds  of  Aniline  and  Mercuric  Salts. 

Mercuric  chloride  compounds. 

A  compound  of  this  type  was  noted  as  long  ago  as  1842.1  Aniline 
and  mercuric  chloride  in  alcohol  form  a  white  crystalline  compound. 
It  appears  to  have  the  formula  (C6H5NH2)2(HgCI2)3.  (CClHg). 
Boiling  water  decomposes  it  giving  aniline  and  a  yellow  compound 
which  was  not  studied. 

The  most  common  aniline  compound  of  this  type  is  the  white 
crystalline  substance  obtained  from  the  alcoholic  mother  liquors  from 
the  action  of  aniline  and  mercuric  chloride.2  The  substance  has  the 
composition  (C6H5NH2)2.HgCl2  and  probably  consists  of  one  molecule 
of  mercuric  chloride  added  to  two  amino  groups  in  much  the  same  way 
that  two  molecules  of  hydrochloric  acid  would  add.  Another  com- 
pound C6H5NH2.HgCl2  has  been  obtained.3  A  still  different  kind  of 
compound  has  been  obtained  in  acid  solution,  C6H5NH2.HCl.HgCl2.4 


,  J.  prakt.  Chem.  (1)  27  (1842),  150.  A.  W.  von  Hofmann,  Ann.  47  (1843), 
62.  Ann.  chim.  phys.  (3)  9  (1843),  173. 

2  Schiff,  Compt.  rend.  56  (1863),  492.  Forster,  Ber.  1  (1874),  294.  Ann.  175 
(1875),  25.  Gmelin,  Organische  Chem.  4th  Ed.  II  716.  Andr£,  Compt.  rend.  11? 
(1891),  996.  Pesci,  Z.  anorg.  Chem.  15  (1897),  215. 

1  Schiff,  loc.  cit.     Andr6,  loc.  cit. 

«Swan,  Am.  Chem.  J.  20  (1898),  618. 

205 


206  COMPOUNDS  OF  MERCURY 

Many  other  double  compounds  of  aniline  are  discussed  in  the  Hand- 
buch  of  Gmelin-Kraut-Friedheim-Peters.5 

Mercuric  bromide  compounds. 

The  compound  (CGH5NH2)2.HgBr2  is  made  by -heating  the  com- 
ponents together.    It  can  be  crystallized  from  alcohol.    M.P.  110-12°. 
It  is  decomposed  by  boiling  water.6    Another  mercuric  bromide  com- 
pound of  aniline  is  known,  C6H5NH2.HgBr2.    M.P.  124°. 7 
Mercuric  iodide  compounds. 

The  compound  (C6H5NH2)2.HgI2,  M.P.  60°  (53°),  may  be  crystal- 
lized from  alcohol  containing  a  trace  of  aniline.  It  is  decomposed  by 
pure  alcohol  giving  mercuric  iodide.8  Another  compound,  C6H5NH2. 
HgI2  is  obtained  from  mercuric  iodide  and  a  boiling  alcoholic 
solution  of  aniline.  It  forms  yellow  crystals  which  are  decomposed 
by  hot  alcohol.  It  is  insoluble  in  water  but  easily  soluble  in  aniline 
and  in  alcohol  containing  aniline.9 

Mercuric  nitrate  compounds.10 

Aniline  poured  into  a  mercuric  nitrate  solution  gives  a  white  precipi- 

(O  TT    \ 
HeH5  )N03."    Boiling  with 

water  causes  the  loss  of  some  aniline  nitrate  and  the  formation  of  a 
dense  white  Crystalline  powder,  "N^  g3  ^  JN03.5H20."  Boiling  this 
substance  for  several  days  causes  the  elimination  of  more  aniline  ni- 
trate with  the  formation  of  "N(^5)N03.H20."  Boiling  for  eight 

days  more  gives  no  further  change.  The  three  compounds  obtained 
react  at  once  with  sulfides  but  do  not  react  with  bases  or  iodides. 

Mercuric  nitrite  compounds,  (C6H5NH2)2.Hg(N02)2.  " 
Mercuric  cyanide  compounds. 

Aniline  and  hot  aqueous  mercuric  cyanide  give  a  crystalline  prod- 
uct. This  is  unstable  even  at  80°.  It  gives  no  action  with  alkalies  or 

8V-II  913-15. 

•Klein,  Ber.  13  (1880),  385.     Staronka,  Chem.  Zentr.  1910  II  1743. 

T  Staronka,  loc.  cit. 

•Klein,  loc.  cit.  Staronka,  loc.  cit.  Frangois,  Compt.  rend.  121  (1895),  254,  768. 
J.  pharm.  chim.  (6)  3  (1895),  49.  Chem.  Zentr.  1896  I  470. 

»Vohl,  Arch.  Pharm.  (2)  148  (1871),  201.  Jahresler.  1871,  705.  ScMff,  Compt. 
rend.  56  (1863),  493. 

™Schiff,  Compt.  rend.  56  (1863),  491. 

."Jtay,  J.  Ch&m.  Soc.  101   (1912),  618. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES      207 

iodides.    It  gives  no  color  on  heating,  thus  differing  from  most  aniline 
mercuric  salts.12 

Mercuric  sulfite  compounds. 

C6H5NH2.HgH2(S03)2.H20  forms  white  lamella?.     (Hg,S02,  Ani- 
line).13 

Mercuric  chlorate  and  perchlorate  compounds  are  amorphous  precipi- 

tates.14 

Mercuric  acetate  compounds.15 

Mercurous  nitrate  compounds. 

Aniline  and  mercurous  nitrate  form  a  white  crystalline  powder, 

('  C*  TT    \ 
Hglj  JN03,"  which  gives  metallic  mercury  readily  on  heating.16 


Mercurous  chloride  does  not  act  on  aniline  at  100°,  at  150°  it  gives 
fuchsin. 

N-Mercury  Derivatives  of  Aniline. 

While  mercuric  oxide  will  not  react  with  aniline  the  latter  will 
react  with  "nascent"  mercuric  oxide  forming  N-mercurianiline, 
(C6H5NH-)2Hg. 

N-Mercurianiline,  C6H5NH  —  Hg  —  NHC6H5.  17 
Preparation  and  Properties. 

A  clear  aqueous  solution  of  pure  aniline  prepared  from  acetanilide 
is  treated  with  small  portions  of  sodium  hydroxide  and  mercuric  chlo- 
ride. A  crystalline  powder  is  filtered  off  and  washed  with  water  con- 
taining a  little  aniline.  The  product  is  dried  over  sulfuric  acid.  It 
forms  microscopic  octahedra.  It  gives  a  strong  alkaline  reaction  and 
has  a  strong  caustic  taste.  It  is  decomposed  by  ordinary  solvents. 
The  only  possible  -solvent  is  potassium  hydroxide  solution  containing 
a  small  amount  of  aniline.  Even  this  solvent  cannot  be  used  above 
80°  without  decomposing  the  product. 

2  Schiff,  loc.  cit.     Staronka,  loc.  cit. 
8  Denigfcs,  Compt.  rend.  112  (1891).  805. 
*  Hofmann,  Ber.  38  (1905),  2002. 

8  Gmelin-Kraut-Friedheim-Peters  Handbuch,  V-II  969. 
8  Schiff,  loc.  cit. 

T  Schiff,   loc.    cit.      Pesci,    Qagz.   chim.   ital.  22  I   (1892),  373.     Z.  anorg.  Ghent.  1,5 
(1897),  214. 


208  COMPOUNDS  OF  MERCURY 

Various  formulas  were  assigned  to  this  substance  before  the  correct 
one  was  discovered.18 

Reactions. 

1.  With  acids. 

Acids  in  excess  form  aniline  salts  and  mercuric  salts.  A  small 
amount  of  acid  forms  the  compound  in  which  mercury  is  substituted 
for  hydrogen  of  the  nucleus.  This  reaction  probably  consists  in  the 
removal  of  the  mercury  from  the  nitrogen  forming  a  mercuric  salt 
which  then  mercurates  the  nucleus.19 

2.  With  mercuric  salts. 

Mercuric  acetate  reacts  with  N-mercurianiline  forming  p-amino- 
phenylmercuric  acetate.  The  mechanism  of  this  reaction  has  not  been 
studied.20 

3.  With  sulfur  compounds. 

N-Mercurianiline  reacts  with  carbon  disulfide  forming  thiocarbani- 
lide  and  mercuric  sulfide.  With  thiourea  it  forms  dicyandiamide,  and 
with  thiocarbanilide  it  forms  triphenyl  guanidine.  The  first  two  re- 
actions run  spontaneously  at  room  temperature.21 

"Phenylated  White  Precipitate," 

Wislicenus  before  1875  found  that  the  treatment  of  alcoholic  ani- 
line with  mercuric  chloride  gives  not  only  the  common  soluble  com- 
pound (C6H5NH2)2.HgCl2,  but  also  a  yellowish  white  extremely  in- 
soluble compound  of  the  composition  C6H6NClHg.  Forster  made  an 
exhaustive  study  of  this  substance  and  concluded  that  it  is  a  phenyl 
derivative  of  infusible  white  precipitate,  NH2  —  HgCl.  It  would  thus 
have  the  structure,  C6H5NH  — HgCl  or  possibly  C6H5N  =  Hg.HCl.22 
Pesci  came  to  the  conclusion  that  Forster's  compound  was  identical 
with  the  chloride  obtained  from  the  action  of  aniline  and  mercuric  ace- 
tate followed  by  treatment  with  sodium  chloride  in  the  presence  of 

"Pesci,  Atti  accad.  Lincei,  (5)  I  (1892),  312.  Gaez.  chim.  ital.  22  I  (1892),  373. 
Ohem.  Zentr.  1892  II  213.  Gkusz.  chim.  ital.  23  II  (1893),  529;  27  I  (1897),  568; 
28  II  (1898),  442.  Z.  anorg.  Chem.  15  (1897),  213. 

"Pesci,  Gazz.  chim.  ital.  22  I   (1892),  378;  27  I   (1897),  569;  28  II   (1898),  443. 

20  Pesci,  Oazz.  chim.  ital.  27  I   (1897),  567.     Chem.  Zentr.  1897  II  482. 

"Pesci,  Oazz.  chim.  ital.  27  I  (1897),  572.  Chem.  Zentr.  1897  II  482.  Montecchi, 
Gazz.  chim.  ital.  28  II  (1898),  434.  Chem.  Zentr.  1899  I  381.  Pesci,  Z.  anorg.  Chem. 
15  (1897),  214. 

?2 Forster,  Ann.  175  (1875),  29.    Per.  7  (1874),  294, 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     209 

acetic  acid.  Pesci  used  an  incorrect  formula  for  this  substance  but 
Dimroth  later  showed  that  it  is  probably  a  polymer  of  the  crystalline 
p-aminophenylmercuric  chloride  which  is  obtained  in  the  absence  of 
acetic  acid.23  The  compound  obtained  by  Pesci  and  by  Dimroth 
undoubtedly  has  mercury  attached  to  carbon  but  its  identity  with 
Forster's  compound  has  by  no  means  been  proved. 

"Phenylated  white  precipitate"  is  insoluble  in  all  organic  solvents. 
It  is  purified  by  exhaustive  extraction  with  boiling  alcohol.  It  may  be 
identical  with  the  yellow  insoluble  substance  mentioned  by  Hof- 
mann  in  1843.24 

Reactions. 

An  alcoholic  solution  of  thiocarbanilide  reacts  slowly  with  "phenyl- 
ated  white  precipitate"  giving  triphenyl  guanidine.  This  reaction  is 
used  by  Forster  to  prove  that  a  phenylimido  group  is  attached  to 
mercury  in  the  original  substance.  This  proof  loses  some  of  its  force 
when  it  is  recalled  that  thiocarbanilide  will  react  with  substances  like 
lead  chloride  giving  triphenyl  guanidine.  Forster's  line  of  reasoning 
applied  to  this  case  would  "prove"  that  lead  chloride  contains  a  phenyl- 
imido group  attached  to  lead.  In  spite  of  this  apparent  flaw  Forster's 
reasoning  may  be  correct  as  white  precipitate  itself  reacts  with  thio- 
carbanilide forming  diphenyl  guanidine.  A  reaction  which  gives  bet- 
ter support  to  the  N  —  Hg  structure  is  the  action  of  "phenylated  white 
precipitate"  with  monophenyl  thiourea  to  form  alpha-diphenyl  guani- 
dine.25 

"Phenylated  white  precipitate"  reacts  with  iodine  forming  iodani- 
line  and  diiodaniline.26  This  reaction  has  no  value  in  settling  the 
structure  of  the  substance  as  the  same  products  would  be  given  by  an 
N  —  Hg  and  a  C  —  Hg  compound. 

Andre  was  unable  to  make  a  substance  having  the  composition  of 
Forster's  phenylated  white  precipitate.27  His  analyses  are  C  16.3, 
H  1.47,  Cl  15.0,  Hg  64.4,  N  2.64,  figures  which  agree  fairly  well  with  a 
formula  (G6H5NH  — HgCl)5(HgCl2)2.  Long  boiling  of  this  gives  a 
substance,  (C6H5NH  —  HgCl)  8.  (HgCl2)  2. 

Mercury  acetamide  and  aniline  hydrochloride  in  water  solution 

23  Pesci,  Z.  anorg.  Chem.  15   (1897),  214.     Dimroth,  Bev.  35   (1902),  2037. 

24  A.  W.  von  Hofmann,  Ann.  47   (1843),  62. 

"Forster,  loc.  cit.     Byk,  J.  prakt.  Chem.  (2)  20  (1879),  335. 
29  Rudolph,  Ber.  11   (1878),  78. 
"  Compt.  rend.  112  (1891),  997. 


210  COMPOUNDS  OF  MERCURY 

give  a  yellow  precipitate  which  is  soluble  in  an  excess  of  the  hydro- 
chloride  solution.  If  enough  of  the  hydrochloride  is  used  a  white 
crystalline  precipitate  of  (C6H5NH2)2.HgCl2  is  formed.  The  yellow 
precipitate  corresponds  to  the  formula  C6H5NH  —  HgO  —  HgCl.28 
Franklin  suggests  that  this  substance  may  have  the  structure, 

HgOH 
/ 
C6H5N  . 29    Aniline  itself  reacts  with  mercury  acetamide  giv- 

HgCl 

ing  a  viscous  solid.30 

True  Organic  Mercury  Derivatives  of  Aniline. 

p-Aminophenylmercuric  Acetate. 
Preparation.31 

1.  From  N-mercurianiline  and  acetic  acid. 

2.  From  N-mercurianiline    and  a   concentrated  solution  of   aniline 

acetate. 

3.  From  N-mercurianiline  and  mercuric  acetate  solution. 

4.  From  aniline  acetate  and  mercuric  oxide. 

5.  From  aniline  and  mercuric  acetate. 

One  or  two  molecules  of  aniline  can  be  used.  Mercuric  acetate 
dissolved  in  water  is  treated  with  freshly  distilled  aniline.  On  short 
standing  thick,  hard,  slightly  yellow  prisms  separate.  After  standing 
three  hours  these  are  filtered  off.  They  consist  of  the  practically  pure 
para  compound.  On  longer  standing  more  of  these  prisms  separate 
mixed  with  small  crystals  of  the  ortho  compound.  Yield  40  gm.  of 
para  compound  and  3  gm.  of  ortho  compound  from  18.6  gm.  of  pure 
aniline  treated  with  31.8  gm.  of  mercuric  acetate. 

Properties. 

p-Aminophenylmercuric  acetate  forms  colorless  thick  prisms  when 
pure.  (CHHg).  M.P.  167°.  It  is  insoluble  in  water  and  ether,  very 

"Ftirth,  Monatsh.  23   (1902),  1157. 

2»  Franklin,  Am.  Chem.  J.  47   (1912),  361. 

8°Forster,  J.  Chem.  Soc.  73   (1898),  795.     Chem.  News  78  (1898),  250. 

"Pesci,  Atti  accad.  Lincei  (5)  1  (1892),  312.  Gazz.  chim.  ital.  22  I  (1892),  373. 
Chem.  Zentr.  1892  II  213.  Piccinini  and  Ruspaggiari,  Gasz.  ohim.  ital.  22  II  (1892), 
604.  Pesci,  Gazz.  chim.  ital.  27  I  (1897),  573.  Chem.  Zentr.  1897  II  482.  Pesci, 
Z.  anorg.  Chem.  15  (1897),  215.  Reitzenstein  and  Bonitsch,  J.  prakt.  Chem.  (2)  86 
(1912),  76.  Dimroth,  Ber.  35  (1902),  2039. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     211 

difficultly  soluble  in  alcohol  and  chloroform.  It  can  be  crystallized 
from  the  latter  solvent.  It  has  basic  properties  turning  red  methyl 
orange  yellow.  It  is  said  to  be  readily  soluble  in  dilute  acids.32  It  is 
soluble  in  a  water  solution  of  aniline  acetate.  It  is  also  soluble  in  di- 
lute bases.  Concentrated  potassium  hydroxide  gives  a  compound  of 
composition  C6H5NHg. 

Reactions. 

1.  With  chlorides. 

When  the  pure  acetate  is  treated  with  aqueous  sodium  chloride 
solution,  it  is  changed  to  a  corresponding  chloride  which  is  crystalline 
and  fairly  soluble  in  the  common  organic  solvents.  If,  however,  the 
reaction  is  carried  out  in  the  presence  of  acetic  acid  by  dissolving  the 
acetate  in  acetic  acid  and  then  adding  the  chloride  solution,  an  isomeric 
chloride  is  obtained  which  is  amorphous  and  extremely  insoluble  in 
common  solvents.33  The  amorphous  chloride  may  be  a  polymer  of  the 
crystalline  chloride.  It  was  obtained  in  the  same  way  by  Pesci  who 
did  not  obtain  any  of  the  crystalline  form.34  He  believed  it  to  be 
identical  with  the  "phenylated  white  precipitate"  obtained  by  Forster 
from  boiling  alcoholic  solutions  of  aniline  and  mercuric  chloride.35 

2.  With  bromides. 

Ammonium  bromide  gives  p-aminophenylmercuric  bromide.    M.P. 

182o   36 

3.  With  iodides. 

The  acetate  reacts  with  potassium  iodide  in  such  a  way  that  a  small 
amount  of  ionic  mercury  enters  the  solution.  This  has  not  been  ex- 
plained. The  chief  product  is  p-aminophenylmercuric  iodide.  M.P. 
165°. 

The  following  reactions  involve  the  amino  group  without  changing 
the  acetoxymercuri  group: 

4.  Acetylatlon. 

Treatment  with  cold  acetic  anhydride  gives  p-acetoxymercuriacet- 
anilide,  CH3CONH  —  C6H4  —  HgOAc.  The  white  powder  can  be 
recrystallized  from  hot  water  from  which  it  separates  in  leaflets. 

82  Jacobs  and  Heidelberger,  J.  Biol.  Chem.  20  (1915),  515,  find  this  statement  of 
Dimroth  to  be  untrue. 

"Dimrotti,  Ber.  35   (1902),  2040. 

**Gazz.  cMm.  ital.  28  II  (1898),  445. 

*5Ann.  175   (1875),  25. 

"Piccinini,  Ga-zz.  chim.  ital.  24  II  (1894),  457.     Ber.  28  R   (1895),  113. 


212  COMPOUNDS  OF  MERCURY 

(CHHg).  It  softens  at  220°  and  melts  at  2210.37  It  is  identical  with 
the  compound  obtained  from  acetanilide  and  mercuric  acetate.38 

5.  With  aldehydes. 

Salicylaldehyde  in  absolute  alcohol  reacts  with  the  powdered  ace- 
tate giving  a  mercurated  Schiff  s  base, 

AcOHg  —  C6H4  —  N  =  CH  —  C6H4  —  OH. 

It  forms  deep  yellow  microcrystals,  soluble  in  dilute  sodium  hydroxide, 
chloroform,  and  acetic  acid.  It  is  hydrolyzed  with  difficulty  by  boiling 
dilute  hydrochloric  acid.  (NHg) .  On  rapid  heating  it  darkens  at  140° 
and  melts  with  decomposition  at  185 °.39 

6.  Diazotization  and  coupling. 

p-Aminophenylmercuric  acetate  can  be  diazotized  in  the  usual  way. 
The  solution  of  the  diazonium  salt  gives  coupling  reactions  with  phenol, 
dimethylaniline,  diethylaniline,  resorcin,  and  alpha-naphthylamine-5- 
sulfonic  acid.  The  mercurated  azo  dyes  obtained  in  this  way  are  rather 
insoluble  substances  of  high  melting  or  decomposition  points.  The 
alkaline  solutions  dye  silk  yellow  or  orange.40 

7.  With  dinitrophenyl  pyridine  chloride. 

The  mercurated  aniline  reacts  the  same  as  aniline  itself.  The 
product  is 

AcOHg  -  C6H4  -  N  =  (CH)  5  -  NH2C1  -  C6H4  -  HgOAc. 

(CHN).  M.P.  164°.  It  is  insoluble  in  common  solvents.  If  the  reac- 
tion is  carried  out.  in  boiling  alcohol  the  dinitraniline  formed  reacts 
with  one  of  the  acetoxymercuri  groups  giving  a  product  containing  the 
linkage  C  —  Hg  —  N  which  is  probably 

AcOHg  -  C6H4  -  N  =  (CH)  5  -  NH2C1  -  C6H4  -  Hg-NH-C0H3  (NO2)  2. 

(CHNHg).  M.P.  244°.  It  is  insoluble  in  all  common  solvents.  The 
mother  liquor  gives  a  small  amount  of  a  substance  which  is  said  to  be 

AcOHg  -  C6H4  -  N  =  (CH)  5  -  NH2C1  -  C6H4  -  HgOH. 

(N).  It  blackens  at  180°  but  does  not  melt  at  250°.  It  seems  highly 
improbable  that  the  molecule  of  HC1  would  remain  attached  to  the 

"Dimroth,  B&r.  35  (1902),  2039. 

"Pesci,  aaez.  chim.  ital.  24  II  (1894),  449;  29  I  (1899),  397. 
88  Jacobs  and  Heidelberger,  J.  Biol.  Chem.  20  (1915),  518. 
40  Ibid. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     213 

second  nitrogen  in  the  formula  instead  of  reacting  with  the  strongly 
basic  —  HgOH  group.41 
8.     With  propargyl  acetal.42 

When  the  substances  are  boiled  in  alcohol  for  six  hours  the  acetal 
odor  disappears.  When  the  yellow  solution  is  acidified  with  dilute 
hydrochloric  acid  a  light  yellow  powder  is  obtained.  This  blackens 
and  decomposes  at  180°.  The  analyses  agree  with  no  formula. 

If  the  reaction  is  carried  out  in  cold  acetic  acid  a  small  amount  of  a 
yellow  precipitate  is  obtained  which  gives  a  nitrogen  analysis  in 
agreement  with  the  formula 

AcOHg  -  C6H4  -  NH  -  CH  =  CH  -  CH  =  N  -  C6H4  -  HgOAc.HOAc. 
p-Mercuribis-aniline,  (NH2  —  C6H4  — )  2Hg. 
Preparation. 

1.  p-Aminophenylmercuric  acetate  or  hydroxide  is  treated  with 
caustic  alkali  and  then  with  sodium  sulfide  giving  mercuric  sulfide  and 
the  desired  compound.43 

2.  Finely   powdered   p-aminophenylmercuric    acetate   is   warmed 
with  concentrated  sodium  thiosulfate  solution  until  dissolved.    A  small 
amount  of  mercuric  sulfide  separates.     This   is  quickly   filtered  off 
and  the  filtrate  is  cooled.     White  crystals  separate.     These  are  re- 
crystallized  from  a  little  hot  water.    A  little  more  mercuric  sulfide 
separates.    The  crystals  are  sodium  p-aminophenylmercuric  thiosulfate, 
NH2  —  C6H4  —  HgS  —  SO3Na.     (CHNaHg).    M.P.  95°  with  decom- 
position.    On  standing,  the  substance  turns  brown  and  then  black. 
When  heated  with  water  for  some  time  it  forms  p-mercuribis-aniline.44 

3.  p-Aminophenylarsenious  oxide,  NH2  —  C0H4  —  AsO,  is  heated 
with  sodium  hydroxide  and  mercuric  chloride.45 

4.  p-Mercuribis-acetanilide  (CH3CONH  —  C6H4  — )  2Hg,  is  heated 
with  alcoholic  potassium  hydroxide  at  100°  ,46 

Properties. 

p-Mercuribis-aniline  forms  colorless  needles  soluble  in  chloroform, 
very  little  soluble  in  alcohol  and  benzene,  insoluble  in  ether.  M.P.  174° 
decomp. 

41  Reltzen stein  and  Stamm,  J.  prakt.  Chem.  (2)  81  (1910),  151. 

42  Reitzen stein  and  Bonitsch,  J.  prakt.  Chem.   (2)  86  (1912),  77. 
«Pesci,  Qazz.  chim.  ital.  23  II   (1893),  529;  28  II   (1898),  446. 
"Piccinini,  loc.  cit.     Dirnroth,  Ber.  35   (1902),  2042. 

48  D.  R.  P.  272,289.     Frankel,  Arzneimittelsyntliese,  4th  Ed.  1919,  p.  661. 
"Pesci,  Z.  anorg.  Chem.  15   (1897),  223. 


214  COMPOUNDS  OF  MERCURY 


p-Aminophenylmercuric  hydroxide  and  its  anhydride,  HN — C6H4 — Hg 
or  HN  ==  C6H4  =Hg. 

Various  formulas  have  been  assigned  to  the  basic  substance  ob- 
tained from  p-aminophenylmercuric  acetate  and  concentrated  bases. 

Preparation. 

1.  p-Aminophenylmercuric  acetate  dissolved  in  dilute  potassium 
hydroxide  and  then  treated  with  30  per  cent  potassium  hydroxide 
gives  a  precipitate  of  the  hydroxide  or  its  anhydride.47 

2.  A  solution  of  mercuric  nitrate  added  to  an  acid  solution  of  ani- 
line nitrate  gives  an  immediate  precipitate  of  white  leaflets.    Boiling 
water  changes  these  to  a  compound  which  is  soluble  in  dilute  potassium 
hydroxide.    When  this  solution  is  treated  with  concentrated  potassium 
hydroxide  a  precipitate  of  the  anhydride  is  obtained.     (CHHg)  ,48 

Properties. 

The  anhydride  forms  colorless  plates  which  become  opaque  on 
standing  in  air.  It  has  a  strong  alkaline  reaction  and  caustic  taste. 
It  is  very  little  soluble  in  water,  insoluble  in  ether.  It  combines  readily 
with  acids  giving  salts  of  p-aminophenylmercuri.  It  decomposes  on 
heating. 

Reactions. 

1.  With  sulfides.49 

The  anhydride  is  suspended  in  water  and  treated  with  the  calcu- 
lated amount  of  sodium  sulfide.  After  heating  for  some  time  the  pre- 
cipitate is  filtered  off  and  dried.  It  is  then  powdered  and  extracted 
with  hot  chloroform  to  remove  the  p-mercuribis-aniline.  The  residue 
is  mercuric  sulfide. 

2.  With  methyl  iodide  and  sulfides.50 

The  finely  powdered  anhydride  is  suspended  in  methyl  alcohol  and 
allowed  to  stand  with  methyl  iodide  in  the  cold  for  24  hours.  Then  a 
little  potassium  hydroxide  in  methyl  alcohol  is  added  and  the  mix- 
ture is  refluxed  for  a  few  hours.  A  yellow  crystalline  powder  forms. 
This  is  treated  with  barium  sulfhydrate  giving  a  quarternary  ammo- 

«7Pesci,  Z.  anorg.  Chem.  15   (1897),  214.     Dimroth,  Ber.  35    (1902),  2044. 
«8Piccinini  and  Ruspaggiari,   Qvzz.  chim.  ital.  22  II   (1892),  609. 
48Pesci,  Gazz.  chim.  ital.  23  II   (1893),  529.     Chem.  Zentr.  1894  I  501.     Ber.  27  R 
(1894),  128. 

MPesci,  loc.  cit.     Dimroth,  Ber.  35  (1902),  2044. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     215 

nium  compound  of  p-mercuribis-aniline.    The  changes  involved  may 
be  indicated  as  follows: 

CH3I,  KOH 
(NH2  —  C6H4-HgOH)  -  — »  I(CH3)3N  — C6H4-HgI 

Ba(SH)2 

— *HgS  +  Hg[C6H4-N(CH3)3I]2 

The  product  is  the  same  as  that  obtained  from  p-mercuribis-dimethyl- 
aniline  and  methyl  iodide. 

p-Aminophenylmercuric  chloride. 

This  substance  exists  in  two  forms,  an  amorphous  insoluble  form, 
and  a  crystalline  form  which  is  fairly  soluble  in  organic  solvents. 
Preparation  of  the  amorphous  chloride.51 

p-Aminophenylmercuric  acetate  dissolved  in  acetic  acid  is  treated 
with  sodium  chloride  solution. 

Preparation  of  the  crystalline  chloride.52 

The  finely  powdered  acetate  is  boiled  with  a  large  volume  of  water 
containing  a  slight  excess  of  sodium  chloride.  The  hot  solution  is 
filtered.  On  cooling  shining  leaflets  separate.  These  can  be  recrystal- 
lized  from  alcohol  or  benzene. 

Properties  of  the  amorphous  form. 

It  is  a  pale  yellow  precipitate  insoluble  in  all  solvents,  and  dilute 
acids.  (CHClHg).  It  is  slightly  soluble  in  potassium  hydroxide.  It 
is  said  to  be  identical  with  Forster's  "phenylated  white  precipitate." 

Properties  of  the  crystalline  chloride. 

If  forms  shining  leaflets  which  are  soluble  in  hot  alcohol  and  ben- 
zene. (CHNHg).  M.P.  1880,53  2400.54  The  former  is  probably  correct. 

Reactions. 

1.    With  aniline  hydrochloride.55 

The  amorphous  chloride  dissolves  in  an  alcoholic  solution  of  aniline 
hydrochloride.  On  cooling  it  deposits  crystals  which  decompose  above 
150°  and  are  identical  with  Gerhardt's  compound  (C6H5NH2)2.HgCl2.56 

"Pesci,  Z.  anorg.  Chem.  15   (1897),  208.     Dimroth,  Ber.  35   (1902),  2041. 

"Dimroth,  loc.  cit.     Reitzenstein  and  Stamm,  J.  prakt.  Chem.  (2)   81   (1910),  156. 

63  Dimroth,  loc.  cit. 

54  Reitzenstein  and  Stamm,  loc.  cit. 

B8Pesci,  loc.  cit. 

M  Chimie  organique,  III  86. 


216  COMPOUNDS  OF  MERCURY 

The  identity  is  proved  by  the  fact  that  both  compounds  when  boiled 
with  water  give  the  compound  (C6H5NHHgCl)2.HgCl2.  (CHNClHg). 

2.  With  sodium  thiosulfate.57 

Both  the  amorphous  and  crystalline  chlorides  react  with  concen- 
trated sodium  thiosulfate  giving  sodium  p-aminophenylmercuric  thio- 
sulfate which  on  heating  gives  p-mercuribis-aniline. 

3.  With  dinitrophenyl  pyridine  chloride.58 

The  reaction  in  boiling  alcohol  gives  a  red  brown  powder  to  which 
is  assigned  the  formula 
ClHg-C6H4-N  =  CH-CH  =  CH-CH  =  CH-NH2Cl-C6H4-HgOH. 

(CHNClHg).  M.P.  125°.  It  seems  unlikely  that  the  molecule  of 
hydrochloric  acid  would  react  with  the  nitrogen  forming  a  hydro- 
chloride  instead  of  reacting  with  the  —  HgOH  group  forming  —  HgCl. 
If  the  reaction  is  carried  out  in  cold  acetone  solution,  an  unhydro- 
lyzed  product  is  obtained.  This  is  a  red  brown  powder  melting  at 
151°.  It  is  insoluble  in  common  solvents.  It  is  believed  to  have  the 
formula 

ClHg  —  C6H4  —  N  =  (CH)  B  —  NH2C1  -  C6H4  —  HgCl. 
(CHNClHg). 

4.  With  propargyl  acetal.59 

When  the  substances  are  refluxed  in  benzene  a  light  yellow  pre- 
cipitate is  obtained  which  darkens  at  160°  and  melts  at  190°.  No 
formula.  If  the  reaction  is  carried  out  in  a  water  suspension  on  the 
steam  bath  a  yellow  solid  is  obtained  which  sinters  at  210°  but  gives 
no  definite  melting  point.  No  formula  is  given  for  it. 

5.  With  ethoxyacrolein  acetal,  C2H50  —  CH  =  CH  —  CH  (OC2H5)  2.60 
The  two  substances  are  warmed  on  the  water  bath  until  no  more 

alcohol  is  evolved.  A  dark  brown  liquid  and  a  smeary  precipitate  are 
formed.  The  solid  can  be  recrystallized  from  some  of  the  acetal.  It 
darkens  at  160°  and  melts  at  190°.  Analyses  for  chlorine  and  mer- 
cury agree  fairly  well  with  the  formula 

ClHg  —  C6H4  —  NH  —  CH  =  CH  —  CH  (OC2H5)  2. 

BT  Dimroth,  loc.  cit. 

M  Reitzenstein  and  Stamm,  loc.  cit. 

59  Reitzenstein  and  Bonitsch,  J.  prakt.  Chem.   (2)   86  (1912),  78. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     217 

p-Aminophenylmercuric  bromide. 

The  acetate  is  dissolved  in  dilute  acetic  acid  and  treated  with  po- 
tassium bromide  solution.  The  product  is  a  slightly  yellow  precipitate 
which  is  amorphous  and  insoluble  in  water  and  common  solvents.  It 
is  insoluble  in  acids  but  slightly  soluble  in  bases.  (Hg).  M.P.  182°. 

p-Aminophenylmercuric  iodide.6'1 

A  solution  of  the  acetate  in  acetic  acid  is  precipitated  by  dilute 
potassium  iodide  solution.  The  product  is  amorphous  and  insoluble  in 
water,  common  solvents,  acids,  and  alkalies.  (IHg).  M.P.  165°. 

Apparently  no  attempt  has  been  made  to  secure  the  bromide  or 
iodide  in  crystalline  soluble  forms  corresponding  to  that  obtained  with 
the  chloride  when  it  is  prepared  in  the  absence  of  acetic  acid. 

p-Aminophenylmercuric  nitrate. 

The  nitrate  may  be  obtained  directly  from  mercuric  nitrate  and  a 
solution  of  aniline  nitrate.  It  forms  white  leaflets.62 

The  nitrate  can  also  be  obtained  from  an  acetic  acid  solution  of  the 
acetate  treated  with  sodium  nitrate  solution.  The  white  flakey  crystals 
are  insoluble  in  water  but  soluble  in  acids  and  bases.  Boiling  water 
changes  it  to  a  compound,  uC6H5NHg.HN03.C6H5NH2.HN03".63 

p-Aminophenylmercuric  acid  sulfate. 

The  acetate  suspended  in  water  and  treated  with  50  per  Cent  sul- 
furic  acid  gives  a  mass  of  colorless  needle  crystals  which  are  insoluble 
in  water,  common  solvents,  acids,  and  bases.  It  decomposes  at  150° 
without  melting. 

Sodium  p-aminophenylmercuric  thiosulfate, 

NH2  —  C6H4  —  HgS  —  S03Na. 64 

The  acetate  is  suspended  in  water  and  treated  with  warm  concen- 
trated sodium  thiosulfate  solution  until  all  dissolves  except  a  little 
mercuric  sulfide.  This  is  filtered  off  and  the  filtrate  is  cooled  until 
colorless  plates  separate.  These  are  quickly  recrystallized  from  a 
small  amount  of  water.  M.P.  95°  decomp.  The  substance  turns  brown 

61  Pesci,  loc.  cit.  and  Z.  anorg.  Chem.  32  (1902),  231.  Piccinini,  loc.  cit.  Dimroth, 
loc.  cit.  and  Z.  anorg.  Chem.  33  (1903),  314.  Brieger  and  Schulemann,  J.  prakt.  Chem. 
(2)  89  (1914),  104. 

82  Piccinini  and  Ruspaggiari,  loc.  cit. 

"Pesci,  Gazz.  chim.  ital.  22  I  (1892),  380. 

"Dimroth,  Ber.  35   (1902),  2042. 


218  COMPOUNDS  OF  MERCURY 

or  black  on  standing  due  to  the  separation  of  mercuric  sulfide.  The 
other  product  of  the  decomposition  is  p-mercuribis-aniline.  The  same 
change  can  be  brought  about  more  rapidly  by  heating  the  thiosulfate 
with  water.  The  thiosulfate  can  also  be  made  from  the  amorphous 
and  crystalline  p-aminophenylmercuric  chlorides.  (CHNaHg) . 

o-Aminophenylmercuric  acetate.65 

A  small  amount  of  the  ortho  compound  is  obtained  from  the  mother 
liquor  from  the  para  compound.    In  properties,  it  resembles  the  para 
compound  closely  but  is  more  soluble.    It  forms  pearly  leaflets  from 
dilute  alcohol.    (CHN).    M.P.  158-60°. 
Reactions. 

1.  With  sodium  chloride. 

Only  one  o-aminophenylmercuric  chloride  is  obtained.  It  is  crystal- 
line and  fairly  soluble.  This  result  is  in  sharp  contrast  to  that  ob- 
tained with  the  para  compound  which  occurs  in  two  forms. 

2.  Acetylation. 

Cold  acetic  anhydride  gives  a  clear  solution.  Crystals  of  o-ace- 
toxymercuri  acetanilide  are  obtained.  M.P.  156-8°.  This  substance 
reacts  with  bromine  giving  o-bromacetanilide  melting  at  99°  (Br). 
This  proves  the  position  of  the  mercury  in  the  nucleus. 

3.  With  dinitrophenyl  pyridine  chloride. 

Short  heating  of  the  substances  in  acetone  gives  a  red  precipitate 
which  gives  a  nitrogen  analysis  in  agreement  with  the  formula 

AcOHg-C6H4-N=  (CH)  5-NH2Cl-C6H4-Hg-NH-C6H3  (NO2)  2. 
o-Aminophenylmercuric  chloride. 

The  mother  liquor,  from  the  preparation  of  p-aminophenylmercuric 
acetate  from  aniline  and  mercuric  acetate,  is  treated  with  sodium  chlo- 
ride solution  to  form  a  mixture  of  the  insoluble  amorphous  parachlo- 
ride  and  the  orthochloride  which  is  soluble  in  hot  alcohol.  The 
amorphous  p-chloride  remains  after  the  extraction  with  alcohol.  The 
orthochloride  forms  long  colorless  plates  from  alcohol  or  acetic  acid. 
(CHHg). 
%-Amino-5-nitrosophenylmercuric  chloride.65* 

The  corresponding  mercurated  p-nitrosophenol  is  warmed  for  half 
an  hour  on  the  water  bath  with  ammonium  chloride,  acetate,  and  car- 

"Dimroth,  loc.  cit.     Reitzenstein  and  Bonitsch,  J.  prakt.  Chem.   (2)   86  (1912),  76. 
<"*Kharasch  and  Piccard,  J.  A.  O.  8.  42  (1920),  1855. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     219 

bonate.  A  slight  brown  precipitate  is  formed.  This  is  dried  in  vacuo 
and  crystallized  from  anisole.  It  is  slightly  soluble  in  benzene,  gives 
a  green  solution  in  ether,  and  a  reddish  yellow  solution  in  alcohol. 
(NClHg). 

2,  4-Diacetoxymercuri  aniline,  (AcOHg)2C6H3  —  NH2. 66 
Preparation. 

Aniline  is  treated  with  two  molecules  of  mercuric  acetate  in  aqueous 
solution.  After  standing  two  days  white  crystals  begin  to  separate. 
These  are  purified  by  suspending  in  water,  adding  ammonium  acetate, 
and  then  ammonium  hydroxide  to  dissolve  the  crystals.  After  filter- 
ing, the  solution  is  treated  with  acetic  acid  until  practically  neutral 
and  then  set  aside  for  12  hours.  The  white  precipitate  is  extracted 
with  hot  water  slightly  acid  with  acetic  acid.  The  ammonium  hy- 
droxide purification  is  repeated. 

Properties. 

The  dimercurated  aniline  forms  white  crystals.  (CHNHg).  M.P. 
206°.  It  is  soluble  in  acetic  acid,  very  little  in  hot;  water,  and  insoluble 
in  alcohol.  It  dissolves  in  ammonium  hydroxide,  probably  forming  a 
compound  of  some  kind. 

Reactions. 

Refluxing  the  acetate  with  acetic  anhydride  for  12  hours,  adding 
water,  and  cooling  gives  white  crystals  of  2,  J^-dmcetoxymercuriacetani- 
lide.™  This  can  be  purified  by  dissolving  in  ammonium  acetate  and 
ammonium  hydroxide  and  then  precipitating  by  acetic  acid.  (Hg). 
When  the  dimercurated  acetanilide  is  treated  with  bromine  in  acetic 
acid  the  product  is  2,  4-dibromacetanilide  melting  at  146°. 

When  the  diacetate  is  dissolved  in  a  -large  amount  of  water  and 
treated  with  dilute  sodium  hydroxide  a  white  substance  slowly  sepa- 
rates. It  is  2,  4-dihydroxymercurianiline.  (Hg).  It  decomposes  at 
250°  without  melting.  It  is  very  little  soluble  in  hot  water  and  in- 
soluble in  alcohol. 

M  Vecchiotti,  Gazz.  cMm.  ital.  44  II   (1914),  35.     Chem.  Zentr.  1914  II  1350. 
87  Cf.  Pesci,  Chem.  Ztg.  23   (1899),  58. 


220  COMPOUNDS  OF  MERCURY 

Theory  of  the  Mechanism  of  the  Mercuration  of  Aromatic  Amines.63 

It  has  been  suggested  that  the  mercuration  of  aromatic  amines  is 
always  preceded  by  the  addition  of  the  inorganic  mercury  compound 
to  the  amino  nitrogen  forming  an  ammonium  salt  in  which  the  posi- 
tive group  — HgX  is  attached  to  nitrogen.  This  group  then  re- 
arranges to  the  ortho  or  para  position  in  the  ring  in  the  same  way 
that  the  chlorine  of  N-chloroacetanilide  rearranges  to  give  p-chloro- 
acetanilide.  That  such  preliminary  addition  is  necessary  for  mercu- 
ration is  practically  proved  by  the  fact  that  substituted  anilines,  such 
as  p-nitro-dimethylaniline  and  p-nitro-diethylaniline,  which  are  too 
weakly  basic  to  form  stable  hydrochlorides,  cannot  be  mercurated  by 
treatment  with  mercuric  acetate  in  aqueous  alcohol.  The  corre- 
sponding monoalkyl  anilines  which  do  form  hydrochlorides  can  be 
mercurated  in  the  usual  way.  Moreover,  the  ortho  and  met  a  nitro- 
dimethylanilines  form  hydrochlorides  and  can  be  mercurated.  An- 
other case  which  supports  the  theory  is  that  of  trimethylphenyl  am- 
monium acetate.  This  substance  obviously  cannot  add  a  molecule 
of  mercuric  salt.  It  "gives  no  action  with  mercuric  acetate  and  alcohol 
either  on  standing  for  months  or  on  boiling  for  twenty- four  hours. 

Mercury  Compounds  from  the  Nitroanilines.69 

The  three  nitroanilines  react  with  mercuric  acetate  in  methyl  alco- 
hol giving  colored  precipitates  which  are  blackened  at  once  by  ammo- 
nium sulfide.  Long  standing  in  contact  with  the  mother  liquor  changes 
these  precipitates  to  substances  which  are  stable  to  ammonium  sul- 
fide. 

Recently  more  work  has  been  done  on  the  mercury  derivatives  of 
the  nitroanilines.70  The  ortho  and  para  compounds  react  with  mer- 
curic acetate  in  cold  alcohol  solution  forming  precipitates  of  a  deep 
maroon  color.  This  color  is  explained  by  formulating  the  substances 
as  ortho  and  para  quinone-imide-acinitro  salts, 


=  C6H1  =  N-0-)2Hg. 

M  Kharasch  and  Jacobsohn,  J.  Am.  Chem.  Soc.  43  (1921),  May  ? 

"Rother,  Dissert.  Berlin,  1911,  p.  19. 

70  Private  communication,  Kharasch,  Lommen,  and  Jacobsohn. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     221 

This  seems  more  likely  than  the  older  formulation  of  the  substances 
as  N  —  Hg  compounds.71  Meta-nitroaniline  under  similar  conditions 
gives  a  slightly  yellow  compound  which  probably  consists  of  a  mer- 
curic acetate  "salt"  of  the  aniline,  N02  — C6H4  — NH2.Hg(OAc)2. 

If  the  reactions  are  carried  out  in  boiling  alcohol,  mercuration  of  the 
nucleus  takes  place.  Ortho  nitroaniline  reacts  with  one  or  two  mole- 
cules of  mercuric  acetate  giving  4-acetoxymercuri-£-nitroaniline  and 
4,  6-diacetoxymercuri-%-nitroaniline.  Both  these  compounds  are 
orange  yellow  in  color.  Treatment  with  sodium  hydroxide  changes 
them  to  bright  scarlet  compounds.  These  probably  have  a  quinoid 
structure.  Para  nitroaniline  gives  two  products,  ®-acetoxymercuri-4- 
nitroaniline  and  2,  6-diacetoxymercuri-4-nitroaniline.  These  com- 
pounds turn  maroon  red  on  treatment  with  sodium  hydroxide.  The 
former  compound  reacts  with  acetic  anhydride  giving  2-acetoxymer- 
curi-4-nitroacetanilide,  a  colorless  substance.  Treatment  of  the  mer- 
curated  aniline  with  sodium  thiosulfate  gives  2,  2' -mercuribis-4-nitro- 
aniline.  Meta  nitroaniline  gives  two  compounds,  4-acetoxymercuri-3- 
nitroaniline  and  4,  6-diacetoxymercuri-8-nitroaniline.  The  former 
compound  is  yellow  and  the  latter  is  reddish  purple. 

Mercury  Derivatives  of  Monomethylaniline.72 

p-Methylaminophenylmer curie  acetate,  CH3NH —  C6H4  —  HgOAc. 

An  aqueous  alcoholic  solution  of  mercuric  acetate  is  treated  with  an 
alcoholic  solution  of  monomethylaniline.  The  product  consists  of  color- 
less transparent  leaflets  which  are  insoluble  in  water  and  ether,  easily 
soluble  in  hot  alcohol  and  dilute  acetic  acid.  M.P.  149°  decomp. 

Treatment  with  acetic  acid  and  sodium  nitrite  gives  a  mercurated 
nitrosamine,  AcOHg  —  C6H4  —  N(NO)CH3.73  M.P.  183-4°  decomp. 
(corr.)  (NHg).  The  formation  of  this  nitrosamine  proves  that  the 
original  mercury  compound  is  a  secondary  amine  and  disproves  Pesci's 
bimolecular  formulas.74 

p-Methylaminophenylmercuric  hydroxide. 

The  acetate  is  treated  with  potassium  hydroxide  with  the  formation 
of  an  amorphous  white  powder  insoluble  in  common  solvents.  When 

"Jackson  and  Peakes,  Am.  Chem.  J.  39  (1907),  567. 

"Pesci,  Gazz,  chim.  ital.  23  II  (1893),  521.  Chem.  Zentr.  1894  I  501.  Gazz. 
chim.  ital.  23  II  (1893),  529.  Ber.  27  B  (1894),  128.  Pesci,  Z.  anorg.  Chem.  15 
(1897),  216. 

78  Jacobs  and  Heidelberger,  J.  Biol.  Chem.  20   (1915),  513. 

"Cf.  Dimroth,  Ber.  35   (1902),  2039  ff. 


222  COMPOUNDS  OF  MERCURY 

heated  with  sodium  sulfide  it  gives  p-mercuribis-monomethylaniline, 
Hg(C6H4  —  NHCH,)2.  Treatment  with  methyl  iodide  and  then  with 
potassium  hydroxide  and  barium  sulfhydrate  gives  the  compound, 
Hg[C6H4  —  N(CH3)3I]2,  which  is  the  same  as  that  obtained  from 
the  para  mercury  compounds  of  aniline  and  dimethylaniline. 

p-Methy laminop heny Imer curie  chloride . 

The  acetate  is  treated  with  sodium  chloride  solution.  M.P.  108°  de- 
comp.  It  is  an  amorphous  slightly  yellow  powder  which  is  insoluble  in 
water  and  alcohol.  It  turns  green  in  light.  The  bromide  is  made  in 
the  same  way  and  has  similar  properties.  M.P.  120°  decomp.  The 
nitrate  is  made  from  the  acetate  and  a  large  amount  of  cold  dilute 
nitric  acid.  It  forms  colorless  hexagonal  leaflets  which  dissolve  in  hot 
water  with  decomposition.  On  heating  it  decomposes  suddenly  at  150°. 
The  sulfate  is  prepared  from  the  acetate  by  means  of  dilute  sulfuric 
acid.  It  forms  microscopic  prisms  which  are  soluble  in  dilute  sulfuric 
acid.  M.P.  130°  decomp. 

p-Mercuribis-monomethylaniline. 

The  hydroxide  is  treated  with  the  calculated  amount  of  sodium  sul- 
fide, heated,  filtered,  washed,  dried,  and  extracted  with  hot  benzene. 
The  product  forms  colorless  needles  which  are  little  soluble  in  alcohol, 
soluble  in  benzene,  insoluble  in  ether.  (CHHg).  M.P.  179°. 

Monomethylaniline  and  aqueous  mercuric  chloride  give  a  yellowish 
precipitate  which  forms  yellow  needles  from  alcohol.  No  formula  is 
given.75 

p-Nitro-o-acetoxymercuri-monomethylaniline.™ 

p-Nitro  monomethylaniline  in  alcohol  is  boiled  with  an  aqueous  so- 
lution of  nine-tenths  of  a  mole  of  mercuric  acetate.  The  product  is 
extracted  with  ether  to  remove  unchanged  material.  The  residue  is 
crystallized  from  alcohol.  A  small  amount  of  a  dark  red  solid  re- 
mains insoluble.  It  has  not  been  studied.  The  product  forms  small 
yellow  crystals.  It  is  soluble  in  acetone  and  in  hot  alcohol  containing 
a. few  drops  of  glacial  acetic  acid.  (NHg).  M.P.  197°  decomp.  Treat- 
ment with  concentrated  potassium  hydroxide  gives  a  brick  red  com- 
pound. Dilution  restores  the  yellow  color.  The  corresponding  chlo- 
ride is  obtained  from  the  mother  liquors  of  the  acetate  by  the  addition 

"Lachowicz,  Monatsh.  10   (1889),  893. 

T6Kharasch  and  Jacobsohn,  J.  Am.  Chem.  Soc.  43   (1921)   May? 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     223 

of  sodium  chloride  solution.  The  product  forms  pale  yellow  crystals 
which  are  soluble  in  acetone  and  in  boiling  alcohol.  (Cl).  M.P.  215° 
decomp.  Treatment  with  one  molecule  of  bromine  gives  no  definite 
product.  Two  molecules  form  4-nitro-2,  6-dibromomonomethylaniline 
melting  112-13°. 

Mercury  Derivatives  of  Dimethylaniline. 

p-Mercuribis-dimethylaniline. 
Preparation. 

1.  From  p-bromodimethylaniline  and  sodium  amalgam.77 

2.  From  p-dimethylaminophenylmercuric  hydroxide  and  sodium  sul- 

fide.78 

The  finely  powdered  hydroxide  is  suspended  in  water  and  treated 
with  the  calculated  amount  of  sodium  sulfide.  After  several  hours' 
heating  the  gray  precipitate  is  filtered  off,  dried,  and  extracted  with 
hot  benzene  leaving  black  flakes  of  mercuric  sulfide.  The  benzene 
solution  on  cooling  gives  colorless  needles. 

It  is  an  interesting  fact  that  the  R2Hg  compound  is  not  obtained 
by  heating  p-dimethylaminophenylmercuric  iodide  with  an  excess  of 
alcoholic  potassium  iodide.  Considerable  dimethylaniline  is  obtained.79 
This  result  is  quite  different  from  that  obtained  with  a  compound  hav- 
ing the  mercury  ortho  to  the  dimethylamino  group.  o-Iodomercuri-p- 
bromo-dimethylaniline  reacts  with  potassium  iodide  giving  the  corre- 
sponding mercuribis  compound  in  good  yield.80 

Properties. 

p-Mercuribis-dimethylaniline  separates  from  benzene  in  shining 
needle  crystals  containing  one  molecule  of  benzene  which  is  lost  on 
standing  in  air.  It  is  little  soluble  in  alcohol  and  ether,  readily  soluble 
in  chloroform.  (CHHg).  M.P.  169°.  It  is  slightly  soluble  in  cold 
dilute  hydrochloric  acid  and  is  reprecipitated  by  bases. 

Reactions. 

1.    With  acids.81 

Hydrochloric  acid  in  benzene  reacts  in  the  cold  giving  dimethyl- 

"Michaelis  and  Schenck,  Ber.  21   (1888),  1501.     Awn.  260   (1890),  6. 

78Pesci,  Oasz.  chim.  ital.  23  II   (1893),  526.     Chem.  Zentr.  1894  I  501. 

79  Unpublished  results,  Whituiore  and  L.  F.  Howe. 

»°Whitniore,  J.  Am,  Ohem.  Soc.  41   (1919),  1850. 

81Michaelis  and  Schenck,  loc.  cit.    Michaelis  and  Rabinerson,  Ber.  23  (1890),  2342. 


224  COMPOUNDS  OF  MERCURY 

aniline  and  p-dimethylaminophenylmercuric  chloride.  Acetic  acid 
gives  mercuric  acetate  and  dimethylaniline.  The  intermediate  organo- 
mercuric  acetate  is  not  obtained. 

2.  With  mercuric  salts.82 

Mercuric  halides  react  readily  in  alcohol  forming  the  correspond- 
ing p-dimethylaminophenylmercuric  halides. 

3.  With  phosphorus  trichloride.83 

The  reaction  takes  place  spontaneously  with  the  evolution  of  heat 
even  when  diluted  with  benzene.  The  reaction  is  completed  by  heat- 
ing in  a  sealed  tube  for  three  hours  at  130°.  The  products  are  mer- 
curic chloride  and  dimethylaminophosphenyl  chloride, 

(CH3)2N-C6H4-PC12. 

4.  With  thionyl  chloride.84 

The  two  substances  react  on  slight  warming  giving  a  bright  yellow 
voluminous  precipitate.  This  is  probably 

[(CH3)2N-C6H4-]3S-0-Hg-C6H4-N(CHs)2. 

When  this  precipitate  is  boiled  with  concentrated  hydrochloric  acid  all 
the  mercury  appears  in  the  ionic  form.  After  treatment  with  hydrogen 
sulfide  and  filtration  the  filtrate  gives  the  sulfine  chloride, 

[  (CH3)  2N  —  C6H4— ]  3SC1.6H20. 

5.  With  methyl  iodide.85 

The  substances  react  in  the  cold  forming  the  compound, 
Hg[ — C6H4  —  N(CH3)3I]2.  It  forms  colorless  crystals  which  turn 
yellow  at  218°  and  melt  at  230°.  It  is  also  obtained  by  treating  the 
following  substances  with  methyl  iodide  in  methyl  alcohol,  then  with 
alcoholic  potassium  hydroxide,  and  finally  with  barium  sulf hydrate: 
the  anhydride  of  p-aminophenylmercuric  hydroxide,  p-methylamino- 
phenylmercuric  hydroxide,  and  p-dimethylaminophenylmercuric  hy- 
droxide. When  this  quarternary  iodide  is  treated  with  silver  chloride 
and  water  it  gives  a  solution  of  the  corresponding  chloride.  This  re- 
acts with  mercuric  chloride  giving  a  compound  which  melts  with  de- 
composition at  225°.  This  substance  is  given  the  formula  of  a  double 
salt,  Hg[C6H4  —  N(CH3)3Cl]2.HgCl2.  It  would  seem  likely  that  this 

"Michaelis  and  Schenck,  B&r.  21  (1888),  1501.    Ann.  260  (1890),  6.  Michaelis  and 
Babinerson,  Ber.  23   (1890),  2342. 
88  IMd. 

"Michaelis  and  Godchaux,  Ber.  24   (1891),  758. 
"Pesci,  Gassz.  chim.  ital,  23  H   (1893),  528. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     225 

formulation  is  not  correct  and  that  the  product  is  the  result  of  the 
usual  reaction  between  R2Hg  and  HgX2,  namely 
ClHg  —  C6H4  —  N(CH,)8C1. 

p-Dimethylaminophenylmercuric  acetate.86 
Preparation. 

1.  Dimethylaniline  is  treated  with  mercuric  acetate  in  50  per 
cent  alcohol.    Small  needle  crystals  soon  separate.    These  are  recrystal- 
lized  from  hot  alcohol  avoiding  long  heating  which  causes  decompo- 
sition. 

2.  Dimethylaniline  acetate  is  treated  with  mercuric  oxide.87 

Properties. 

The  acetate  forms  long  colorless  needles.  (CHNHg).  M.P.  165°. 
It  is  soluble  in  benzene,  chloroform,  hot  alcohol,  dilute  acids,  but  in- 
soluble in  water.  It  does  not  react  with  cold  ammonium  sulfide. 

Reactions. 

1.  Cold  or  hot  potassium  iodide  in  alcohol  gives  only  the  corre- 
sponding iodide  and  a  very  small  amount  of  inorganic  mercury.88 

2.  Potassium  hydroxide  gives' p-dimethylaminophenylmercuric  hy- 
droxide. 

p-Dimethylaminophenylmercuric  hydroxide. 

The  acetate  treated  with  hot  aqueous  potassium  hydroxide  gives  a 
solution  which  on  cooling  deposits  microscopic  prisms.  (CHNHg) .  M.P. 
179°  with  decomposition  after  turning  yellow  about  150°.  It  is  very 
little  soluble  in  cold  water  but  readily  on  heating.  The  solution  is 
strongly  alkaline.  Treatment  with  13  per  cent  sodium  sulfide  gives 
p-mercuribis-dimethylaniline. 

p-Dimethylaminophenylmercuric  chloride. 
Preparation. 

1.  From  the  acetate  in  acetic  acid  treated  with  sodium  chloride 
solution. 

2.  From  p-mercuribis-dimethylaniline  and  mercuric  chloride  in 
alcohol. 

'•Pesci,  Z.  <morg.  Chem.  15   (1897),  217.     Dimroth,  Ber.  35   (1902),  2044, 
OTPesci,  Gwzz.  chim.  ital.  23  II  (1893),  528. 
88  Dimroth,  Z.  anorg.  Chem.  33   (1903),  314. 


226  COMPOUNDS  OF  MERCURY 

3.  From  p-mercuribis-dimethylaniline  and  a  benzene  solution  of 
hydrogen  chloride. 

Properties  and  reactions. 

The  chloride  gives  white  pearly  leaflets  from  chloroform  in  which 
it  is  difficultly  soluble.  (NClHg).  M.P.  225°.  It  is  almost  insoluble 
in  alcohol,  slightly  soluble  in  benzene  and  chloroform.  It  dissolves 
in  cold  dilute  hydrochloric  acid  and  is  reprecipitated  by  sodium  car- 
bonate. 

The  corresponding  bromide  is  prepared  from  p-mercuribis-dimethyl- 
aniline and  mercuric  bromide  in  alcohol.  It  resembles  the  chloride. 
(NBr).  M.P.  226°.  The  iodide  is  prepared  like  the  bromide  or  by 
treating  the  acetate  with  potassium  iodide.  It  resembles  the  chloride. 
(I).  M.P.  195°. 

Quarternary  ammonium  compounds  related  to  p-mercuribis-dimethyl- 
aniline. 
The  iodide,  Hg[C6H4  — N(CH3)3I]2. 89 

Preparation. 

1.  From  p-mercuribis-dimethylaniline  and  methyl  iodide. 

2.  From    p-dimethylaminophylmercuric    hydroxide    and    methyl 
iodide,  followed  by  treatment  with  barium  sulfhydrate. 

3.  From  p-aminophenyl  mercuric  hydroxide  or  its  anhydride  and 
methyl  iodide,  potassium  hydroxide,  and  barium  sulfhydrate. 

4.  From  p-methylaminophenylmercuric  hydroxide  and  the  same 
reagents. 

In  each  of  the  last  three  preparations  the  first  product  is 
IHg  —  C6H4  —  N(CH3)3I.  This  reacts  with  the  sulfhydrate  giving 
mercuric  sulfide  and  the  corresponding  R2Hg  compound. 

Properties. 

The  quarternary  iodide  forms  fine  colorless  flexible  needles  which 
are  very  little  soluble  in  cold  water,  easily  soluble  in  hot  water  and 
alcohol,  but  insoluble  in  chloroform  and  benzene.  It  is  not  changed 
by  boiling  potassium  hydroxide.  When  heated  slowly  it  turns  brown 
at  218°  and  melts  at  230°.  Rapid  heating  gives  a  lower  melting 
point. 

The  chloride,  Hg[C6H4  —  N(CH3)3C1]2,  is  obtained  in  water  solu- 

89pesci,  Z.  anorg.  GUem.  15  (1897),  218, 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     227 

tion  by  treating  the  iodide  with  silver  chloride.  It  reacts  with  bromine 
giving  mercuric  salts  and  p-bromophenyl  trimethyl  ammonium  chlo- 
ride. With  mercuric  chloride  it  gives  the  "double  salt"  melting  at 
225°  with  decomposition.  The  corresponding  hydroxide  is  obtained 
from  the  iodide  and  silver  oxide.  The  aqueous  solution  is  strongly 
basic  and  caustic.  It  absorbs  carbon  dioxide  rapidly. 

p-Iodomercuriphenyl  trimethyl  ammonium  iodide, 
IHg  —  C6H4  —  N(CH,)SL 

p-Dimethylaminophenylmercuric  hydroxide  is  treated  with  methyl 
iodide  in  cold  methyl  alcohol.  The  iodide  forms  hard  greenish  yellow 
branched  prisms.  It  is  insoluble  in  water,  very  soluble  in  acetone  even 
cold,  difficultly  soluble  in  alcohol.  It  is  best  crystallized  from  alcohol. 
(CHIHg).  M.P.  140°  Treatment  with  barium  sulfhydrate  gives  the 
corresponding  R2Hg  compound,  Hg[C6H4  —  N(CH3)3I]2. 

Mercury  Derivatives  of  p-Bromodimethylaniline.90 

p-Bromodimethylaniline  reacts  readily  with  a  cold  alcoholic  solu- 
tion of  mercuric  acetate  containing  a  little  acetic  acid  to  prevent  the 
alcoholysis  of  the  mercuric  salt.  One  hydrogen  of  the  nucleus  is  re- 
placed by  the  acetoxymercuri  group. 

o-Acetoxymercuri-p-bromo-dimethylaniline. 

The  product  from  the  action  of  mercuric  acetate  on  p-bromodi- 
methylaniline  forms  white  needle  crystals.  It  is  almost  insoluble  in 
water  and  petroleum  ether.  It  is  difficultly  soluble  in  toluene,  ethyl 
ether,  and  chloroform  even  on  heating.  It  is  fairly  soluble  on  heating 
in  ethyl  acetate,  benzene,  and  carbon  tetrachloride.  It  is  very  solu- 
ble on  heating  in  methyl  alcohol,  ethyl  alcohol,  and  acetone.  Carbon 
disulfide  dissolves  it  readily  even  in  the  cold.  It  is  best  crystallized 
from  methyl  alcohol,  ethyl  alcohol,  or  benzene.  The  latter  is  the 
best  solvent  for  its  purification  as  it  does  not  dissolve  the  mercurous 
acetate  which  is  present  as  an  impurity.  It  is  also  soluble  in  cold  con- 
centrated ammonium  hydroxide.  M.P.  144°  (HgBr).  The  acetate 
reacts  very  slowly  with  sulfides.  Its  solution  in  ammonium  hydroxide 
gives  a  white  precipitate  of  the  organomercuric  sulfide  when  treated 
with  hydrogen  sulfide.  This  precipitate  remains  white  for  several 

MWhitmore,  /.  Am.  Chem.  Soc.  41   (1919),  1841. 


228  COMPOUNDS  OF  MERCURY 

hours.  After  standing  for  five  hours  at  room  temperature  it  turns 
gray.  The  acetate  can  be  changed  to  other  salts  by  the  usual  metathet- 
ical  reactions.  The  chloride  separates  from  alcohol  or  benzene  in 
felted  needles.  M.P.  183°  (BrClHg).  The  bromide  crystallizes  in 
larger  needles  than  the  chloride.  It  is  more  soluble  in  organic  solvents. 
M.P.  182°  (Hg).  The  iodide  is  even  more  soluble  than  the  bromide. 
M.P.  169°  (Hg).  The  thiocyanate  resembles  the  halides.  M.P.  135° 
(BrHg) .  The  hydroxide  is  formed  from  the  acetate  and  the  calculated 
amount  of  sodium  hydroxide  in  alcohol.  It  forms  hard  wart-like 
masses  of  crystals  which  are  insoluble  in  all  inert  solvents.  M.P. 
162°  (Hg).  It  dissolves  in  acetic  acid  and  in  ethyl  acetate  giving  back 
the  original  acetate.  The  reaction  of  the  hydroxide  with  an  ester  gives 
a  new  method  for  making  organomercuric  salts  of  organic  acids.  The 
formate  is  made  by  dissolving  the  hydroxide  in  an  excess  of  ethyl 
formate.  On  cooling,  fine  felted  needles  separate.  M.P.  145°  (BrHg). 
The  crystals  turn  black  on  standing.  The  formate  is  more  soluble  than 
the  acetate.  It  is  fairly  soluble  in  water.  Heating  the  formate  in 
benzene  and  alcohol  gives  metallic  mercury,  p-bromodimethylaniline, 
and  a  mere  trace  of  the  corresponding  mercuribis  compound. 

Mercuribis-p-bromo-dimethylaniline  or  2,  &'-mercuribis-4-bromo-di- 
methylaniline. 

It  is  prepared  from  the  acetate  by  refluxing  with  potassium  iodide 
in  alcohol  for  8  hours.  Yield  86  per  cent.  It  forms  white  needle 
crystals.  M.P.  123°  (BrHg).  It  is  more  soluble  than  the  acetate, 
being  soluble  even  in  the  cold  in  benzene,  toluene,  ether,  carbon  disul- 
fide,  and  acetone. 

Treatment  of  the  organomercuric  acetate  with  sodium  thiosulfate 
and  with  sodium  sulfide  gives  smaller  yields  of  the  mercury  diphenyl 
derivative. 

The  mercury  diphenyl  compound  reacts  quantitatively  with  mer- 
curic chloride,  bromide,  iodide,  and  thiocyanate  forming  the  corre- 
sponding R  —  Hg  —  X  compounds. 

Mercury  Derivatives  of  Nitro  Dimethylanilines.91 

Of  the  three  isomeric  nitro  dimethylanilines  the  para  compound 
alone  cannot  be  mercurated  by  means  of  mercuric  acetate.  This 
property  of  the  para  compound  is  connected  with  its  extremely  weak 

"Kharasch  and  Jacobsohn,  J.  Am.  Chem.  Soc.  43  (1921),  May? 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     229 

basic  properties  and  consequent  inability  to  form  salts.  It  seems 
almost  certain  that  the  entrance  of  mercury  into  the  nucleus  of  an 
aromatic  amine  is  preceded  by  the  formation  of  a  "salt"  by  the  addition 
of  the  inorganic  mercury  compound  to  the  amino  nitrogen.  The  posi- 
tive —  HgX  group  then  rearranges  to  the  nucleus  in  much  the  same 
way  as  does  the  chlorine  in  N —  chloroacetanilide. 

o-Nitro-p-acetoxymercuri-dimethylaniline. 

o-Nitro  dimethylaniline  dissolved  in  a  small  volume  of  alcohol  is 
boiled  with  nine-tenths  of  a  mole  of  mercuric  acetate.  In  half  an  hour 
a  side  test  with  ammonium  sulfide  gives  no  black  precipitate.  A  small 
amount  of  mercurous  acetate  is  removed  by  filtering  the  hot  solution. 
Crystals  separate  on  cooling.  The  product  is  yellow  and  is  soluble  in 
the  common  organic  solvents.  (NHg).  M.P.  160°.  The  corresponding 
chloride  is  obtained  by  treating  the  filtrate  from  the  original  reaction 
mixture  with  sodium  chloride  solution.  The  product  is  red  and  amor- 
phous. (NCI).  M.P.  185°  decomp. 

m-Nitro-p-acetoxymercuri-dimethylaniline. 

m-Nitro  dimethylaniline  is  treated  with  mercuric  acetate  in  the 
usual  way.  The  reaction  is  complete  after  half  an  hour's  boiling.  The 
product  forms  brilliant  orange  needles  which  are  soluble  in  the  common 
organic  solvents.  (NHg).  M.P.  140°.  The  chloride  is  obtained  from 
the  mother  liquor  in  the  usual  way.  It  is  red  and  amorphous  (Cl). 
M.P.  220°  decomp. 

Mercury  Derivatives  of  Monoethylaniline.92 

p-Mercuribis-monoethylaniline. 

The  finely  powdered  hydroxide,  C2H5NH  —  C6H4  —  HgOH,  is 
heated  with  the  calculated. amount  of  sodium  sulfide  solution.  The  dark 
precipitate  is  dried  and  extracted  with  boiling  xylene.  The  extracts 
on  cooling  give  colorless  crystals  of  the  mercury  diphenyl  derivative. 
These  are  fairly  soluble  in  benzene  and  slightly  soluble  in  alcohol. 
(CHHg).  M.P.  166°. 

p-E thy laminophenylmer curie  acetate. 

An  alcohol  solution  of  monoethylaniline  is  treated  with  a  solution  of 
mercuric  acetate  in  dilute  alcohol.  Colorless  transparent  prisms  sepa- 
rate which  are  insoluble  in  cold  water,  easily  soluble  in  benzene,  prac- 

•*  Pesci,  loc.  cit. 


230  COMPOUNDS  OF  MERCURY 

tically  insoluble  in  ether.    (CHHg).    M.P.  130°.   The  acetate  is  ap- 
parently decomposed  by  hot  water. 

p-Ethylaminophenylmercuric  hydroxide. 

The  acetate  is  treated  with  potassium  hydroxide  on  the  water  bath. 
The  clear  solution  deposits  colorless  heavy  needles  on  cooling.  It  is 
little  soluble  in  cold  water,  soluble  hot,  but  insoluble  in  ether.  The 
water  solution  has  a  strong  alkaline  reaction.  (CHHg) .  It  decomposes 
at  145°  without  melting. 

Treatment  with  sodium  sulfide  changes  the  hydroxide  to  p-mercuri- 
bis-monoethylaniline.  An  excess  of  methyl  iodide  gives  a  yellow 
powder  which  >  probably  IHg  — C6H4  — N(CH3)2(C2H5)I.  When 
this  is  treated  with  barium  sulfhydrate  it  gives  the  corresponding  R2Hg 
compound,  Hg[C6H4  — N(CH3)2(C2H5)I]2. 

p-Ethylaminophenylmercuric  chloride. 

The  acetate  is  treated  with  calcium  chloride  in  alcohol.  The  chlo- 
ride is  recrystallized  from  alcohol  from  which  it  forms  colorless  hex- 
agonal tablets.  (Hg).  M.P.  143°.  It  is  insoluble  in  cold  water  and 
decomposed  by  hot  water. 

Quarternary  ammonium  compounds  related  to  p-mercuribis-monoethyl- 

aniline. 

The  iodide,  Hg[C6H4  — N(CH3)2(C2H5)I]2  is  prepared  as  just  de- 
scribed. It  forms  long  colorless  silky  needles.  (CHIHg).  M.P.  202°. 
It  can  be  crystallized  from  hot  water.  Hot  bases  have  no  effect  on  it. 
The  corresponding  chloride  is  made  by  treating  the  iodide  with  silver 
chloride.  It  forms  long  colorless  needles  which  are  readily  soluble 
in  water.  The  chloride  gives  a  "double  salt"  with  mercuric  chloride 
which  melts  at  169°  and  is  slightly  soluble  in  alcohol  but  is  insoluble 
in  cold  water.  This  substance  may  very  likely  be  a  true  organomer- 
curic  salt,  ClHg  — C6H4  — N(CH3)2(C2H5)C1.  The  hydroxide, 
Hg[C6H4  — N(CH3)2(C2H5)OH]2,  is  made  from  a  water  solution  of 
the  iodide  and  silver  oxide.  The  resulting  solution  is  strongly  basic 
and  caustic.  It  absorbs  carbon  dioxide  readily. 

Mercury  Derivatives  of  p-Nitro  Monoethylaniline.93 

p-Nitro-o-acetoxymercuri-monoethylaniline. 

p-Nitro  monoethylaniline  is  treated  with  mercuric  acetate  in  aque- 
ous alcohol  in  the  usual  way.  The  product  crystallizes  from  alcohol 

wRharasch  and  Jacobsohn,  J.  Am.  Chem.  Soc.  43   (1921),  May? 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     231 

in  small  yellow  crystals.  It  is  soluble  in  acetone.  (NHg).  M.P.  183°. 
Treatment  with  concentrated  potassium  hydroxide  gives  a  brick  red 
compound  which  turns  yellow  on  dilution. 

The  easy  mercuration  of  the  p-nitro  monoethylaniline  is  in  sharp 
contrast  to  the  fact  that  the  corresponding  p-nitro  cfo'ethylaniline  can- 
not be  mercurated.  This  difference  is  due  to  the  difference  in  the  basic 
properties  of  the  two  substances.  p-Nitro  diethylaniline,  like  p-nitro 
dimethylaniline,  does  not  form  salts  readily.  The  monoalkylated  com- 
pounds do  form  salts  and  can  be  mercurated. 

The  corresponding  chloride  is  prepared  from  the  mother  liquor  in 
the  usual  way.  It  is  an  amorphous  yellow  solid.  (Cl).  It  is  soluble  in 
acetone  and  in  hot  alcohol.  M.P.  218°  decomp.  Treatment  with  bro- 
mine gives  4-nitro-2,  6-dibromomonoethylaniline  identical  with  the 
product  obtained  by  the  direct  bromination  of  p-nitro  monoethyl- 
aniline. 

Mercury  Derivatives  of  Diethylaniline. 

p-Mercuribis-  die  thy  laniline.9* 
Preparation. 

1.  From  diethylaminophenylmercuric  hydroxide  and  the  calculated 
amount  of  sodium  sulfide  heated  for  several  hours  on  the  water  bath. 
The  precipitate  is  dried  and  extracted  with  hot  benzene. 

2.  From  p-diethylaminophenylmercuric  chloride  and  an  excess  of 
concentrated  sodium  thiosulfate  solution.95 

3.  From  p-bromodiethylaniline  and  sodium  amalgam. 

Properties. 

It  forms  colorless  efflorescent  prisms  which  are  soluble  in  ether,  in- 
soluble in  alcohol,  fairly  soluble  in  benzene.  (CHHg).  M.P.  160.6°. 
When  treated  with  methyl  iodide  it  gives  the  corresponding  quarter- 
nary  ammonium  compound. 

p-Diethylaminophenylmercuric  acetate. 

Diethylaniline  is  treated  with  mercuric  acetate  in  the  usual  way. 
The  product  crystallizes  from  alcohol  in  long  colorless  needles  which 
are  insoluble  in  water,  soluble  in  ether,  alcohol,  and  dilute  acetic  acid, 
very  soluble  in  benzene.  M.P.  104.4°  (not  164°).  It  decomposes  with 
evolution  of  gas  at  182°. 

MPescl,  loc.  cit. 

••Pigorini,  Gvez.  cMm.  ital.  24  II  (1894),  465.    Ber.  28  B  (1895),  114. 


232  COMPOUNDS  OF  MERCURY 

p-Diethylaminophenylmercuric  hydroxide. 

The  acetate  is  treated  with  potassium  hydroxide  in  the  usual  way. 
The  product  turns  brown  at  125°  but  does  not  melt  (165°?).  It  reacts 
with  sodium  sulfide  forming  p-mercuribis-diethylaniline.  With  methyl 
iodide  and  methyl  alcohol  it  forms  a  yellow  powder  from  which  barium 
sulfhydrate  forms  the  compound,  Hg[C6H4 —  N(CH3)  (C2H5)2I]2. 

p-Diethylaminophenylmercuric  chloride. 

An  acetic  acid  solution  of  the  acetate  is  treated  with  potassium  chlo- 
ride. The  product  forms  sharp  colorless  needles  which  are  little  soluble 
in  cold  water,  fairly  soluble  hot,  soluble  in  hot  dilute  alcohol.  M.P. 
164.5°  (Hg) .  The  chloride  reacts  with  a  warm  sodium  carbonate  solu- 
tion forming  a  complex  oxide,  [(CH3)2N  — C6H4  — Hg— ]20.96 

Quarternary  ammonium  compounds  related  to  p-mercuribis-diethyl- 
aniline. 

The  iodide,  Hg[C6H4  — N(CH3)  (C£H5)2I]2,  is  prepared  by  treat- 
ing p-diethylaminophenylmercuric  hydroxide  with  methyl  iodide  and 
then  with  barium  sulfhydrate.  It  forms  small  colorless  prisms  which 
are  easily  soluble  in  hot  water,  little  in  cold,  little  in  alcohol,  insolu- 
ble in  ether  and  benzene.  M.P.  203°  decomp.  (CHIHg) .  50  per  cent 
sodium  sulfide  removes  the  mercury  entirely  forming  phenyl  methyl 
diethyl  ammonium  iodide. 

The  corresponding  chloride  is  prepared  from  the  iodide  by  silver 
chloride.  It  forms  good  crystals  which  are  very  deliquescent.  It  re- 
acts with  mercuric  chloride  giving  a  "double  salt"  which  softens  at 
168°  and  decomposes  about  200°.  This  substance  may  be  a  compound, 
ClHg  — C6H4  — N(CH3)  (C2H5)2C1.  The  corresponding  hydroxide  is 
made  from  the  iodide  by  silver  oxide.  It  gives  a  strongly  alkaline 
solution. 

Mercury  Derivatives  of  Acid  Anilides. 

N  —  Hg  Compounds. 

CHO 
/ 

N-Mercuribis-formanilide,  (C6H5  —  N  —  )  2Hg.97 

Alcoholic  solutions  of  formanilide  and  mercuric  bromide  are  mixed 
and  treated  with  the  calculated  amount  of  sodium  ethylate.  The  clear 

96  Pigorini,  loc.  cit. 

"Wheeler  and  McFarland,  Am.  Chem.  J.  18  (1896),  542. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     233 

solution  is  precipitated  by  water.  Colorless  needles  are  obtained  which 
melt  at  194°  (NHg).  When  the  product  is  suspended  in  benzene  and 
treated  with  benzoyl  chloride  a  precipitate  is  formed.  This  is  N-chloro- 
mercurijormanilide,  C6H5  —  N  (HgCl)  —  CO  —  H.  This  compound 
can  also  be  prepared  from  formanilide  treated  with  one  molecule  of 
mercuric  chloride  and  one  molecule  of  sodium  ethylate.  The  corre- 
sponding bromide  and  iodide  are  obtained  by  adding  the  proper  halo- 
gen in  carbon  disulfide  to  N-mercuribisformanilide. 

If  formanilide  in  alcohol  is  treated  with  mercuric  acetate  and 
evaporated  colorless  slender  prisms  separate.  These  can  be  recrystal- 
lized  from  alcohol.  (Hg).  The  product  is  believed  to  be  N-acetoxy- 
mercuriformanilide.  It  might,  however,  be  a  C  —  Hg  compound. 

N-Mercuribis-acetanilide*8 

Acetanilide  is  fused  with  yellow  mercuric  oxide.  The  product  is 
crystallized  from  alcohol  in  small  colorless  needles.  M.P.  215°  de- 
comp.  It  reacts  at  once  with  hydrogen  sulfide.  Acid  chlorides  give 
mixed  anilides  and  probably  the  N  —  HgCl  compound  of  acetanilide. 
It  reacts  with  sodium  thiosulfate,  potassium  iodide,  and  ammonium 
bromide  as  do  all  N  —  Hg  compounds  giving  the  corresponding  in- 
organic base,  a  mercuric  salt,  and  the  N  —  H  compound,  in  this  case, 
acetanilide.  This  reaction  may  be  illustrated  by  potassium  iodide, 
[C6H5  -  N(COCH3)  -  ]2Hg  +  2KI  +  2H20  -» 

2C6H5  —  NH  —  COCH3  +  2KOH  +  HgI2. 
N-Mercuribis-methacetin,  [CH30  — C6H4  — N(COCH3)  — ]2Hg." 

Methacetin  is  treated  with  mercuric  chloride  and  sodium  car- 
bonate. The  product  forms  sharp  colorless  tufted  needles.  (Hg).  M.P. 
191°.  It  reacts  in  the  usual  way  with  sodium  thiosulfate,  potassium 
iodide,  and  ammonium  bromide  giving  the  corresponding  base  and 
methacetin. 

C  —  Hg  Compounds  oj  the  Acid  Anilides. 

p-Mercuribis-acetanilide.100 

The  corresponding  hydroxide,  CH3CO  —  NHC6H4  —  HgOH,  is 
treated  with  the  calculated  amount  of  sodium  sulfide  or  barium  sulf- 

88  Oppenheim  and  Pfaff,  Ber.  1  (1874),  624.  Piccinini,  Gazz.  chim.  ital.  24  II 
(1894),  453.  Chem.  Zentr.  1895  I  335.  Wheeler  and  MeFarland,  Am.  Chem.  J.  18 
(1896),  542.  Wheeler,  Am.  Chem.  J.  18  (1896),  696.  Pesci,  Gazz.  chim.  ital.  27  I 
(1897),  568.  , 

"Prussia,  Gazz.  chim.  ital.  28  II   (1898),  123.     Chem.  Zentr.  1898  II  928. 

100  Pesci,  Gazz.  chim.  ital.  24  II  (1894),  449.  Z.  anorg.  Chem.  15  (1897),  223. 
Gazz.  chim.  ital.  29  I  (1899),  394.  Z.  anorg.  Chem.  32  (1902),  232. 


234  COMPOUNDS  OF  MERCURY 

hydrate.  It  can  also  be  prepared  by  fusing  acetanilide  with  mercuric 
acetate  and  then  treating  the  p-acetoxymercuriacetanilide  so  obtained 
with  sodium  hydroxide  and  sodium  thiosulfate.  It  forms  long  needle 
crystals  which  are  little  soluble  in  alcohol  even  hot,  insoluble  in  ether, 
benzene,  and  chloroform.  M.P.  244-6°.  Alcoholic  potassium  hy- 
droxide in  a  tube  at  100°  gives  p-mercuribis-aniline. 

p-Acetaminophenylmercuric  acetate.101 

A  boiling  aqueous  solution  of  acetanilide  is  treated  with  one  mole- 
cule of  mercuric  acetate  in  small  portions.  The  boiling  is  continued 
until  a  side  test  with  a  base  gives  no  mercuric  oxide.  On  cooling, 
shiny  colorless  plates  separate.  These  are  soluble  in  hot  water,  in- 
soluble in  benzene.  M.P.  218-20°.  The  corresponding  chloride, 
CH3CO  —  NHC6H4  —  HgCl.H20,  is  prepared  from  the  acetate  and 
calcium  chloride  in  alcohol  solution.  It  forms  colorless  microscopic 
needles.  These  are  insoluble  in  water,  more  soluble  in  alcohol.  It 
loses  its  crystal  water  at  110°.  M.P.  250°. 

Acetanilide  fused  with  an  excess  of  mercuric  acetate  gives  various 
highly  mercurated  products.  A  dimercurated  and  a  pentamercurated 
product  have  been  isolated.102 

Mercury  Derivatives  of  Diphenylamine. 

p-Mercuribis-diphenylamine,  Hg(C6H4  —  NH  —  C6H5)2.103 

p-Hydroxymercuridiphenylamine,  C6H5  —  NH  —  C6H4  —  HgOH, 
is  heated  with  concentrated  sodium  thiosulfate  forming  a  white  powder. 
This  is  very  little  soluble  in  methyl  and  ethyl  alcohols,  even  on  boiling. 
It  is  soluble  in  hot  benzene  and  easily  soluble  in  chloroform.  Ligroin 
added  to  the  solution  in  chloroform  causes  the  separation  of  good 
crystals.  (Hg).  M.P.  182.5°. 

p-Hydroxymercuri-diphenylamine. 

The  acetate  obtained  from  diphenylamine  and  mercuric  acetate  is 
ground  into  a  paste  with  concentrated  potassium  hydroxide  and  al- 
lowed to  stand  for  24  hours.  A  white  granular  amorphous  substance  is 
formed  which  is  insoluble  in  all  common  solvents.  It  dissolves  enough 

301Pesci,  Z.  anorg.  Chem.  15   (1897),  222.     Dimroth,  Ber.  35  (1902),  2037. 
102Hoff  and  Rossi,  Chem.  Zentr.  1912  II  2070.     Pesci,   Chem.  Ztg.  23   (1899),  58. 
Chem  Zentr.  1899  I  527. 

108  Prussia,  Gazz.  chim.  ital.  28  II   (1898),  129.     Chem.  Zentr.  1898  II  928. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     235 

in  water  to  give  an  alkaline  reaction.    (Hg) .  It  decomposes  below  200° 
without  melting. 

p-Acetoxymercuri-diphenylamine. 

An  alcoholic  solution  of  diphenylamine  is  added  to  a  solution  of 
mercuric  acetate  in  50  per  cent  alcohol  containing  a  little  acetic  acid. 
Heat  is  evolved  and  the  solution  turns  yellow.  Soon  small  plates  of 
the  acetate  separate.  These  are  recrystallized  from  hot  alcohol.  They 
are  insoluble  in  water,  slightly  soluble  in  methyl  and  ethyl  alcohols, 
and  in  hot  benzene.  (CHHg).  M.P.  178°.  The  corresponding  chloride 
is  made  from  the  acetate  and  calcium  chloride  in  alcohol.  It  is  very 
slightly  soluble  in  methyl  and  ethyl  alcohols,  hot  chloroform,  less 
soluble  in  benzene  and  ether,  insoluble  in  water.  (ClHg).  It  softens 
at  232°  and  decomposes  at  240°  without  melting. 

2,  2',  4,  4' -Tetrachloromercuri- diphenylamine, 

(ClHg)  2C6H3  -  NH  -  C6H3  (HgCl)  ,."* 

Diphenylamine  is  heated  with  mercuric  chloride  and  the  mixture 
is  poured  into  acetic  acid  and  boiled  for  some  time.  The  residue  is 
washed  thoroughly  with  glacial  acetic  acid  to  remove  all  unchanged 
diphenylamine.  The  product  is  a  yellow  amorphous  powder  which 
does  not  melt  at  260°  and  is  insoluble  in  common  solvents.  (NClHg) . 

Boiling  pyridine  gives  mercuric  chloride  and  a  product  which  is 
possibly  a  mercazine,  containing  mercury  and  nitrogen  in  a  six  mem- 
bered  ring.  Treatment  with  sodium  thiosulfate  gives  a  complicated 
compound  containing  mercury  with  both  valences  attached  to  carbon. 
Its  structure  has  not  been  settled. 

Treatment  of  the  tetrachloride  with  a  mixture  of  sulfuric  and  nitric 
acids  gives  a  compound  containing  3  —  HgCl  groups  and  2  nitro  groups 
for  each  diphenylamine  residue.  The  position  of  the  nitro  groups  is 
not  settled.  Treatment  of  this  nitro  compound  with  sodium  thiosul- 
fate gives  a  complicated  substance  which  is  designated  as  "Mercuri- 
bis-3-dinitro(?)  mercazine."  Its  structure  is  not  definitely  known.  It 
is  insoluble  in  all  common  solvents. 

p-Mercuribis-methyldiphenylamine,  Hg[C6H4  —  N(CH3)  — C6H5~L. 

The  corresponding  hydroxide,  C6H5  —  N(CH3)  —  C6H4  — HgOH, 
is  treated  with  a  25  per  cent  sodium  thiosulfate  solution.  The  clear 
solution  soon  becomes  turbid  and  deposits  a  white  powder.  This  is 

1MKharasch  and  Piccard,  J.  Am.  Chem.  Soc.  42   (1920),  1861. 


236  COMPOUNDS  OF  MERCURY 

dried  and  dissolved  in  hot  benzene  in  which  it  is  readily  soluble.  The 
solution  is  cooled  and  treated  with  two  volumes  of  ligroin.  Colorless 
plates  separate.  (Hg).  M.P.  138-9°. 

p-Acetoxymercuri-methyldiphenylamine, 

C6H5  -  N  (CH.)  -  C6H4  -  HgOAc. 

Methyldiphenylamine  is  treated  with  mercuric  acetate  in  the  usual 
way.  The  product  forms  slightly  yellow  crystals  from  hot  alcohol. 
M.P.  128°  (Hg) .  It  is  insoluble  in  water  and  benzene,  slightly  soluble 
in  methyl  and  ethyl  alcohols.  The  corresponding  hydroxide  is  made 
from  the  acetate  and  concentrated  potassium  hydroxide.  It  forms 
a  white  amorphous  powder  insoluble  in  all  solvents. 

Mercury  Derivatives  of  Anilido  Fatty  Acids  and  their  Esters. 

2-Acetoxymercuriphenyl  glycine  ethyl  ester, 

AcOHg  —  C6H4  —  NH  —  CH2C02C2H5.105 
Preparation. 

The  ethyl  ester  of  phenyl  glycine  dissolved  in  methyl  alcohol  is 
stirred  with  one  molecule  of  mercuric  acetate  in  methyl  alcohol  con- 
taining a  little  acetic  acid.  The  cloudy  yellow  oil  which  forms  dis- 
solves on  stirring.  In  10  to  15  minutes  no  mercuric  ions  are  left  as 
shown  by  a  side  test  with  sodium  hydroxide.  On  cooling  the  mixture, 
pale  yellow  crystals  separate.  Yield  82  per  cent.  The  mother  liquors 
give  a  small  amount  of  another  product  which  has  not  been  identified. 
The  acetate  is  recrystallized  from  chloroform. 

Properties. 

The  acetate  forms  pale  yellow  crystals.  After  recrystallization 
from  chloroform,  all  of  the  solvent  must  be  removed.  It  softens  at 
128°  and  melts  at  131°  if  free  from  chloroform.  It  is  easily  soluble 
in  organic  solvents  especially  in  hot  chloroform.  It  dissolves  in  hot 
water  and  on  cooling  separates  as  an  oil. 

Reactions. 

1.    With  halogens. 

Bromine  and  iodine  give  halogenated  phenyl  glycine  esters  which 
melt  at  83°  and  87°  respectively.  As  they  are  probably  the  ortho  com- 
pounds the  ortho  structure  is  assigned  to  the  mercury  compound. 

105  Schoeller  and  Schrauth  and  Goldacker,  Ber.  44  (1911),  1301.  Schoeller  and 
Schrauth,  D.  R.  P.  248,291.  Chem.  Zentr.  1912  II  211. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     237 

2.  With  halide  salts. 

Alcoholic  solutions  of  the  alkali  halides  give  the  corresponding 
—  HgX  compounds. 

3.  Saponification. 

Treatment  with  sodium  hydroxide  and  then  with  acid  gives  the  an- 

Hg  —  0 
/  \ 

hydride  of  2-hydroxymercuriphenyl  glycine,  C6H4  C  =  0. 

\  / 

NH  —  CH2 

2-Chloromercuriphenyl  glycine  ethyl  ester. 

An  alcoholic  solution  of  the  acetate  is  treated  with  the  calculated 
amount  of  sodium  chloride  dissolved  in  water.  More  water  is  added. 
Fine  needles  separate.  The  chloride  is  soluble  in  organic  solvents  espe- 
cially ethyl  acetate.  It  is  best  crystallized  from  methyl  alcohol.  It 
sinters  at  149°  and  melts  at  151°.  Heated  above  its  melting  point  it 
gradually  solidifies  and  then  decomposes  above  200°  (NClHg).  It 
forms  rhombic  tablets  from  ethyl  acetate.  The  corresponding  bro- 
mide is  prepared  like  the  chloride  and  has  similar  properties.  It  sin- 
ters 144°  and  melts  146°  (BrHg)  .  The  iodide  resembles  the  chloride 
and  bromide.  (Hg).  It  sinters  136-7°  and  melts  about  139°. 

Anhydride  of  2-hydroxymercuriphenyl  glycine, 

Hg  —  0 

/  \ 

C6H4  C  =  0 

\  / 

NH  —  CH2 

The  finely  powdered  acetate  is  suspended  in  water  and  heated  with 
one  molecule  of  sodium  hydroxide.  The  solid  turns  bright  yellow  but 
does  not  dissolve.  This  substance  is  probably  the  —  HgOH  compound 
of  the  ester.  Another  molecule  of  sodium  hydroxide  is  added  and  the 
mixture  is  boiled  one  or  two  minutes.  All  dissolves.  The  solution  now 
contains  the  sodium  salt  of  2-hydroxymercuriphenyl  glycine.  This  so- 
lution is  treated  with  1.25  equivalents  of  normal  sulfuric  acid.  A  white 
amorphous  precipitate  forms.  It  is  soluble  in  excess  of  acid  probably 

HgX 


due  to  the  formation  of  salts  of  the  type,  C6H4 

\ 


NH  —  CH?  —  C03H 


238  COMPOUNDS  OF  MERCURY 

Yield  91  per  cent.  The  anhydride  decomposes  at  223°  (corr.  228°) 
(CKNHg).  It  is  soluble  in  one  molecule  of  sodium  hydroxide.  This 
solution  gives  precipitates  with  solutions  of  some  metal  salts.  Pre- 
cipitates are  obtained  with  solutions  of  salts  of  lead,  copper,  iron, 
calcium,  silver,  and  platinum.  The  copper  salt  has  been  purified  and 
analyzed.  It  decomposes  about  190-194°. 

(f)Chloromercuriphenyl  glycine™* 

When  the  compound,  Cl2As  —  C6H4  —  NH  —  CH2C02H,  is  heated 
with  mercuric  chloride  a  white  precipitate  containing  mercury  is 
formed.  It  is  soluble  in  alkali  and  probably  has  mercury  attached  to 
the  nucleus. 

Another  mercury  compound  is  obtained  by  heating  p-arseno- 
phenyl  glycine, 

H02C.CH2  —  NH  —  C6H4  —  As  =  As  —  C6H4  —  NH  —  CH2C02H, 
with  alkali  and  mercuric  oxide.  The  product  is  precipitated  by  the 
addition  of  acid.  It  may  be  the  R2Hg  compound  corresponding  to 
phenyl  glycine. 

a-Anilidopropionic  ethyl  ester  reacts  with  'one  molecule  of  mercuric 
acetate  in  methyl  alcohol  forming  a  monomercurated  product  which 
cannot  be  separated  from  some  di-product  formed  at  the  same  time. 
The  reaction  is  complete  in  20  minutes.  The  crude  acetate  is  very 
soluble  in  organic  solvents. 

(%-Chloromercuriphenyl-a-amino)  propionic  ethyl  ester, 

ClHg  —  C6H4  —  NH.CH  (CH8)  —  C02C2H5.107 
An  alcoholic  solution  of  the  impure  acetate  obtained  from  equal 
molecules  of  mercuric  acetate  and  the  anilido  ester  is  treated  with  the 
calculated  amount  of  sodium  chloride.  The  precipitate  is  recrystallized 
from  80  per  cent  alcohol.  (CHNClHg) .  It  is  only  slightly  soluble  in  or- 
ganic solvents.  M.P.  164°.  The  mercury  is  assumed  to  be  in  the 
ortho  position  by  analogy  to  the  corresponding  phenyl  glycine  com- 
pound. 

(2,  4-Diacetoxymercuriphenyl-a-amino)  propionic  ethyl  ester. 

The  anilido  ester  is  treated  with  two  molecules  of  mercuric  acetate 
in  methyl  alcohol.  The  reaction  is  complete  in  about  one  hour.  The 
yield  of  crude  product  is  about  80  per  cent.  This  consists  of  about 

106  D.  R.  P.  272,289.     Oh&m.  Zentr.  1914  I  1469. 

107  Schoeller,  Schrauth,  and  Goldrfcker,  loc.  cit.  1305. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     239 

equal  amounts  of  a  crystalline  soluble  form  and  an  amorphous  in- 
soluble form  of  the  diacetate.  The  former  is  removed  by  repeated 
extractions  with  hot  methyl  alcohol  containing  a  little  acetic  acid. 
This  solution  is  cooled  to  obtain  crystals.  (CHNHg).  M.P.  184°.  The 
insoluble  substance  has  the  same  melting  point  and  the  same  per- 
centage of  mercury  as  the  crystalline  form.  It  may  be  a  polymer.  The 
two  diacetates  give  the  same  products  when  boiled  with  sodium  chlo- 
ride or  bromide. 

(2,  4-Dichloromercuriphenyl-a-amino)  propionic  ethyl  ester. 

The  diacetate  is  treated  with  the  calculated  amount  of  sodium  chlo- 
ride solution.  The  precipitate  is  purified  by  dissolving  in  ethyl  acetate 
and  precipitating  by  the  addition  of  low  boiling  ligroin.  It  forms  small 
needles.  The  same  product  is  obtained  from  the  amorphous  insoluble 
form  of  the  diacetate  by  boiling  with  dilute  sodium  chloride  for  15 
or  20  minutes.  (Hg).  M.P.  128-130°.  The  corresponding  bromide 
is  prepared  from  the  crystalline  or  the  amorphous  diacetate.  (Hg). 
It  melts  about  128°. 

Anhydride  of  (2,  4-dihydroxymercuriphenyl-a-amino)  propionic  acid. 

The  diacetate  obtained  from  a-anilidopropionic  ethyl  ester  and  two 
molecules  of  mercuric  acetate  is  suspended  in  water  and  boiled  with 
3.25  molecules  of  sodium  hydroxide  to  form  a  clear  solution  and  then 
acidified  with  1.25  equivalents  of  normal  sulfuric  acid.  The  white 
amorphous  solid  decomposes  at  218°  (corr.  223°)  (CHNHg).  The 
anhydride  absorbs  water  readily.  As  this  is  not  usually  true  of  the 
anhydrides  or  inner  salts  of  hydroxymercuri  acids  the  loss  of  water 
in  this  case  may  take  place  between  the  two  —  HgOH  groups  instead 
of  between  the  —  HgOH  group  and  the  carboxyl  group. 

a-Anilidobutyric  ethyl  ester  treated  with  one  molecule  of  mercuric 
acetate  gives  a  dimercurated  compound  and  unchanged  ester.  No 
monomercurated  product  is  obtainable  in  methyl  alcohol  solution. 

(2,  4-Diacetoxymercuriphenyl-a-amino)  butyric  ethyl  ester, 
( AcOHg)  2C6H3  —  NH.CH  (C2H5)  —  C02C2H5. 

The  reaction  of  the  anilido  ester  with  two  molecules  of  mercuric 
acetate  in  dilute  methyl  alcohol  is  complete  in  about  half  an  hour. 
Cooling  gives  a  crystalline  product.  Yield  82  per  cent.  It  is  easily 
soluble  in  methyl  and  ethyl  alcohols,  and  in  chloroform,  but  only 


240  COMPOUNDS  OF  MERCURY 

slightly  soluble  in  other  solvents.    It  is  best  recrystallized  from  methyl 
alcohol.     (CHNHg).    It  sinters  at  150°  and  melts  at  153°. 

(2,  4-Dichloromercuriphenyl-a-amino)  butyric  ethyl  ester. 

The  diacetate  is  treated  with  sodium  chloride.  The  dichloride  is 
easily  soluble  in  common  solvents  especially  on  heating.  It  is  best 
purified  by  dissolving  in  ethyl  acetate  and  adding  low  boiling  ligroin. 
(Hg).  On  rapid  heating  it  softens  at  124°  and  melts  at  126°.  The 
corresponding  dibromide  and  diiodide  are  made  in  the  same  way  and 
have  similar  properties.  Bromide  M.P.  126°,  Iodide  M.P.  119°. 

(2,  4-Dihydroxymercuriphenyl-a-amino)  butyric  acid  and  its  anhy- 
dride. 

The  anhydride  is  prepared  from  the  ester  in  the  usual  way.  Yield 
90  per  cent.  The  anhydride  turns  yellow  at  200°  and  decomposes 
at  205°  (corr.  209°)  (CHNHg).  If  allowed  to  stand  in  the  air  the 
anhydride  absorbs  one  molecule  of  water  in  two  hours  but  gives  no 
further  absorption  on  longer  standing.  As  in  the  case  of  the  propionic 
compound  this  easy  hydration  and  dehydration  may  indicate  that  the 
water  is  lost  between  the  two  hydroxymercuri  groups. 

a-Anilido-isovalerionic  ethyl  ester  reacts  with  mercuric  acetate 
giving  a  dimercurated  product  even  when  an  excess  of  the  ester  is  used. 
No  mono  compound  can  be  obtained. 

(2,  4-Diacetoxymercuriphenyl-a-amino)  isovalerianic  ethyl  ester. 

The  reaction  between  the  anilido  ester  and  two  molecules  of  mer- 
curic acetate  in  dilute  methyl  alcohol  is  complete  in  about  half  an 
hour.  Yield  86  per  cent.  The  product  is  recrystallized  from  methyl 
alcohol.  It  is  soluble  in  ethyl  alcohol  and  in  chloroform,  especially 
on  heating.  (CHNHg).  M.P.  125°.  The  corresponding  chloride  is 
made  from  the  acetate  in  the  usual  way.  M.P.  121°.  The  bromide 
occurs  in  two  forms.  When  the  crude  substance  is  heated  with  ethyl 
acetate  part  of  it  is  precipitated  in  an  amorphous  form.  This  decom- 
poses at  215°.  The  ethyl  acetate  mother  liquors  treated  with  low 
boiling  ligroin  give  crystals  which  melt  at  134°.  The  iodide  is  like  the 
bromide  but  is  slightly  yellow  and  occurs  only  in  a  crystalline  form. 
M.P.  128°.  The  anhydride  is  prepared  in  the  usual  way.  It  resembles 
the  corresponding  butyric  acid  compound  in  absorbing  water  readily 
from  the  air.  (CHNHg).  It  decomposes  at  221°  (corr.  226°). 

The  foregoing  studies  on  the  mercuration  of  alpha  anilido  esters 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     241 

in  dilute  methyl  alcohol  with  one  molecule  of  mercuric  acetate  have 
disclosed  some  interesting  regularities.  The  esters  used  have  the  genr 

R 

/ 

eral  formula  C6H5  —  NH  —  CH  .    When  R  =  H  a  monomercu- 

\ 
C02Et 

rated  product  is  obtained.  If  R  =  CH3  a  mixture  of  mono  and  di- 
products  is  obtained.  If  R  =  C2H5  or  i  —  C3H7  only  disubstitution 
products  can  be  obtained. 

Mercury  Derivatives  of  the  Toluidines. 

Derivatives  of  o-Toluidine.™8 

The  reaction  between  o-toluidine  and  one  molecule  of  mercuric 
acetate  in  dilute  methyl  alcohol  gives  a  product  containing  15  per 
cent  of  mono-  and  85  per  cent  of  dimercurated  compounds. 

S-Methyl-4-aminophenylmercuric  acetate. 

A  solution  of  three  molecules  of  ortho  toluidine  in  alcohol  is  added 
rapidly  to  a  solution  of  mercuric  acetate  in  50  per  cent  alcohol.  The 
precipitate  is  recrystallized  from  50  per  cent  alcohol  and  then  from 
absolute  alcohol  to  separate  it  from  a  small  amount  of  the  dimercu- 
rated product.  It  is  easily  soluble  in  hot  water,  soluble  in  alcohol, 
difficultly  soluble  in  ethyl  acetate.  It  decomposes  in  a  vacuum  at  100°. 
If  put  in  a  bath  at  140°  it  melts  at  145°  (NHg) . 

The  acetate  can  be  diazotized  in  the  usual  way  and  coupled  with 
phenol,  yielding  2-methyl-4-acetoxymercuri-4'-hydroxyazobenzene, 
AcOHg  (CH,)  C6H3  —  N  =  N  —  C6H4OH.  (NHg) . 

3-Methyl-4-aminophenylmer  curie  chloride. 

The  alcoholic  mother  liquor  from  the  preparation  of  the  dimercu- 
rated compound  is  treated  with  sodium  chloride  solution.  The  dried 
precipitate  is  extracted  with  hot  ethyl  acetate  and  then  recrystallized 
from  absolute  alcohol.  It  forms  shining  needles.  (CHClHg).  M.P. 
175°.  When  treated  with  acetic  anhydride  it  gives  a  diacetyl  deriva- 
tive thus  proving  that  the  original  mercury  compound  contained  a 
free  amino  group.109  . 

108  Schoeller,    Schrauth,   and    Rother,    B&r.   45    (1912),   2812.      J.   Rother,    Divert. 
Berlin  1911,  p.  24.     Jacobs  and  Heidelberger,  J.  Biol.  Chem.  20  (1915).  519. 
108  Jacobs  and  Heidelberger,  loc.  cit. 


242  COMPOUNDS  OF  MERCURY 

Diacetoxymercuri-o-toluidine. 

Methyl  alcohol  solutions  of  equal  molecules  of  o-toluidine  and 
mercuric  acetate  react  completely  in  a  few  minutes.  The  chief  product 
is  the  dimercurated  compound.  It  is  recrystallized  from  methyl  alco- 
hol. It  decomposes  223°.  It  is  insoluble  in  most  solvents  except  hot 
methyl  alcohol,  it  dissolves  readily  in  acids,  ammonium  hydroxide, 
amines,  etc.  A  better  yield  is  obtained  by  using  two  molecules  of  mer- 
curic acetate. 

The  diacetate  can  be  changed  to  the  corresponding  chloride,  bro- 
mide, iodide,  and  hydroxide  by  double  decomposition  reactions.  The 
hydroxide  gives  an  anhydride  by  loss  of  water  between  the  NH2 
group  and  one  of  the  —  HgOH  groups.  When  this  anhydride  is  treated 
with  an  excess  of  acetic  anhydride  an  acetylated  diacetate  is  formed, 
(AcOHg)2C6H2(CH3)— NHCOCH3.  This  gives  the  corresponding 
chloride,  bromide,  and  iodide.110 

Dihydroxymercuri-o-toluidine . 

The  diacetate  is  suspended  in  water  and  heated  with  sodium  hy- 
droxide to  about  90°  until  almost  entirely  dissolved.  After  filtering 
the  solution  is  cooled  slowly  giving  colorless  needles.  If  dried  at  100° 
or  in  a  vacuum,  or  even  if  treated  with  absolute  alcohol  it  loses  water 
and  changes  to  an  intense  canary  yellow.  The  molecule  of  water  is 
probably  lost  between  the  amino  group  and  the  ortho  hydroxymercuri 
group.  (Anhydride,  CHNHg.) 

Double  salts  of  o-toluidine  and  mercuric  halides.111 

Derivatives  of  m-Toluidinellz 

No  monomercurated  product  has  been  obtained  from  m-toluidine. 
The  reaction  between  equivalent  amounts  of  m-toluidine  and  mer- 
curic acetate  gives  a  dimercurated  product.  An  excess  of  mercuric 
acetate  gives  a  trisubstitution  product. 

Diace  toxymercuri-m-toluidine . 

Equal  molecules  of  m-toluidine  and  mercuric  acetate  are  allowed 
to  react  in  methyl  alcohol.  The  product  forms  colorless  crystals  which 

110  J.  Bother,  loc.  cit. 

111  Klein,  Ber.  13   (1880),  835.     Lachowicz,  Monatsh.  10  (1889),  892. 

112  Schoeller,  Schrauth,  and  Rother,  Ber.  45   (1912),  2812.     Rother,  Dissert.  Berlin 
1911,  p.  81. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     243 

are  insoluble  in  the  common  solvents  except  methyl  and  ethyl  alcohols. 
It  is  also  soluble  in  dilute  alcohol  and  ammonium  hydroxide.  It  is 
stable  to  ammonium  sulfide.  Double  decomposition  yields  the  corre- 
sponding halides.  Sodium  hydroxide  yields  an  amorphous  hydroxide. 
The  diacetate  melts  at  a  high  temperature  with  decomposition. 
(CHHg).  No  monomercury  compound  is  obtained  from  the  mother 
liquors. 

Triace  toxymercuri-m-  to  luidine . 

m-Toluidine  is  treated  with  a  large  excess  of  mercuric  acetate  in 
dilute  methyl  alcohol.  The  product  is  insoluble  in  common  organic 
solvents.  It  is  soluble  in  ammonium  hydroxide  and  slightly  soluble  in 
water.  Boiling  with  ammonium  sulfide  gives  mercuric  sulfide.  (CHHg) . 

Derivatives  of  p-Toluidine.113 

p-Toluidine  reacts  with  mercuric  acetate  giving  a  monomercury 
product.  Heating  with  a  large  excess  of  mercuric  acetate  gives  a  more 
highly  mercurated  product  which  has  not  been  obtained  pure. 

Ace  toxymercuri-p-  to  luidine . 

A  solution  of  mercuric  acetate  in  50  per  cent  alcohol  is  treated  with 
an  alcoholic  solution  of  p-toluidine.  Leaflets  soon  separate.  After 
two  days  the  product  is  filtered  and  purified  by  dissolving  in  ammonium 
acetate  and  ammonium  hydroxide  and  precipitating  by  acetic  acid.  It 
forms  white  crystals  insoluble  in  water,  soluble  in  benzene,  alcohol, 
ether,  and  ammonium  hydroxide.  (CHHg).  M.P.  184°.  It  can  also  be 
prepared  from  p-toluidine  acetate  and  mercuric  oxide. 

When  an  excess  of  mercuric  acetate  reacts  with  p-toluidine  a  white 
solid  is  obtained  which  reacts  at  once  with  cold  ammonium  sulfide.  It 
may  have  mercury  attached  to  nitrogen  as  well  as  to  the  nucleus.  No 
satisfactory  analyses  have  been  obtained. 

Hydroxymercuri-p-to  luidine . 

The  acetate  dissolves  in  concentrated  potassium  hydroxide  giving 
a  clear  solution  which  slowly  deposits  yellowish  laminae.  The  hy- 
droxide is  insoluble  in  common  solvents.  Heat  turns  it  brown  at  120°. 

113  Pesci,'  Gazz.  chim.  ital.  28  II  (1898),  101.  Z.  anorg.  Ghent,.  17  (1898),  276. 
Reitzenstein  and  Stamm,  J.  prakt.  Chem.  (2)  81  (1910),  159.  Schoeller,  Schrauth, 
and  Rother,  loc.  cit.  Rother,  loc.  cit.  Vecchiotti,  Gazz.  48  II  (1918),  80.  Chem.  Abst. 
13  (1918),  1450. 


244  COMPOUNDS  OF  MERCURY 

M.P.  212-3°.  It  dissolves  enough  in  water  to  give  a  strong  alkaline 
reaction.  (CHHg) .  When  treated  with  sodium  thiosulfate  it  gives  mer- 
curibis-p-toluidine. 

C  h  loromercuri-p  -to  luidine . 

The  acetate  and  calcium  chloride  are  allowed  to  react  in  alcohol. 
The  chloride  forms  prismatic  needles.  It  is  insoluble  in  water,  fairly 
soluble  in  alcohol.  (CHHg).  M.P.  170°. 

Mercuribis-p-toluidine. 

The  hydroxide  is  treated  with  concentrated  sodium  thiosulfate  solu- 
tion in  the  usual  way.  The  product  forms  a  white  powder  which  is 
soluble  in  alcohol  but  insoluble  in  other  solvents.  (CHHg) .  M.P.  156°. 

When  dissolved  in  pyridine  and  treated  with  a  methyl  alcohol  solu- 
tion of  dinitrophenyl  pyridine  chloride  it  gives  a  dark  solution  which 
deposits  a  brown  powder  which  is  soluble  in  acetone  and  chloroform. 
M.P.  1330.114 

Double  salts  of  p-toluidine  and  mercuric  salts.115 

Mercury  Derivatives  of  Dimethyl-p-toluidine.116 

Ace  toxymercuri  dime  thy  l-p-to luidine . 

Dimethyl-p-toluidine  is  treated  with  mercuric  acetate  in  the  usual 
way.  Fine  colorless  needles  gradually  separate.  These  are  recrystal- 
lized  from  boiling  benzene.  It  is  insoluble  in  water,  fairly  soluble  in 
ethyl  alcohol,  very  soluble  in  methyl  alcohol.  (CHHg)'.  M.P.  131.5°, 

Hydroxymercuri  dime  thy  I- p-toluidine. 

The  acetate  is  treated  with  concentrated  potassium  hydroxide.  The 
hydroxide  forms  fine  colorless  needles.  It  is  hardly  soluble  in  cold 
water  but  is  a  little  more  soluble  in  hot  water  especially  in  the  presence 
of  a  trace  of  potassium  hydroxide.  It  is  very  soluble  in  methyl  alcohol 
and  benzene.  (Hg).  It  softens  at  114°  and  melts  at  117°. 

Chloromercuri  dimethyl-p-toluidine. 

The  acetate  is  treated  with  calcium  chloride  in  alcohol.  The  chlo- 
ride forms  fine  needles  which  are  little  soluble  in  alcohol^  soluble  in 

114  Reitzenstein  and  Stamm,  loc.  cit. 

"8  Klein,  Ber.  11  (1878),  1743;  13  (1880),  835.  Leeds,  J.  Am.  Chem.  Soc.  3 
(1881),  147.  Werner,  Z.  anorg.  CTiem.  15  (1897),  20.  Ray,  J.  Chem.  Soc.  101  (1912). 
619. 

118Pesci,  Qazz.  cJwm,.  ital.  28  II  (1898),  103.  Chem.  Zentr.  1898  II  546.  Z.  anorg. 
Chem.  17  (1898),  277. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     245 

benzene,  insoluble  in  water.  (Hg).  M.P.  159°.  The  bromide  and 
iodide  resemble  the  chloride.  Their  melting  points  are  149-50°  and 
126°  respectively.  The  corresponding  nitrate  is  made  from  the  acetate 
by  alcoholic  calcium  nitrate  solution.  It  forms  colorless  needles  which 
are  soluble  in  hot  benzene  and  alcohol.  (Hg).  M.P.  131°. 

Mercuribis-  (dimethyl-p-toluidine) . 

The  hydroxide  is  treated  with  sodium  thiosulfate  solution  in  the 
usual  way.  The  clear  solution  soon  deposits  a  white  precipitate.  It  is 
soluble  in  benzene  and  hot  alcohol.  (Mg,Mol.Wt.)  It  reacts  with  alco- 
holic solutions  of  the  mercuric  halides  and  mercuric  acetate  giving 
the  corresponding  RHg  —  salts. 

Another  preparation  for  this  substance  is  from  bromo-dimethyl-p- 
toluidine  and  ethyl  acetate  and  1.5  per  cent  sodium  amalgam.  This 
preparation  proves  that  the  mercury  in  the  derivatives  of  dimethyl-p- 
toluidine  is  ortho  to  the  dimethylamino  group. 

It  is  stated  that  acetoxymercuri  dimethyl-p-toluidine  dissolves  in 
ammonium  hydroxide  and  forms  the  R2Hg  compound  slowly  on  stand- 
ing.117 This  reaction  is  not  mentioned  in  Pesci's  later  summaries  of 
his  work  and  is  without  parallel  in  the  reactions  of  organic  mercury 
compounds. 

Mercury  Derivatives  of  the  Acid  Toluidides. 

N  —  Hg  Compounds. 

N-Mercuribis-(form-p-toluidide)f 

[CH,  -  C6H4  -  N(CHO)  -  ],Hg.  "8 

Formyltoluidine  is  treated  with  mercuric  bromide  and  sodium  ethyl- 
ate.  The  mixture  is  precipitated  by  water.  (Hg).  It  reacts  with  ben- 
zoyl  chloride  forming  N-chloromercuri  form-p-toluidide  and  the  mixed 
diacylated  toluidine. 

C  —  Hg  Compounds. 
Derivatives  of  o-Acetotoluidide*19 

p-Acetoxymercuri-o-acetotoluidide. 

o-Acetotoluidide  is  refluxed  with  mercuric  acetate  in  water.  The 
reaction  is  complete  in  forty  minutes.  Crystals  appear  on  standing. 

"'Pesci,  Gazz.  28  II   (1898),  106.     Chem.  Zentr.  1898  II  546. 
158  Wheeler  and  McFarland,  Am.  Chem.  J.  18   (1896),  545. 
119  Schoeller,  Schrauth,  and  Rother,  loc.  cit.  2813. 


246  COMPOUNDS  OF  MERCURY 

Yield  28  per  cent.  The  acetate  is  recrystallized  from  80  per  cent, 
alcohol.  (CHHg).  M.P.  228°  (corr.  233°).  When  treated  with  iodine 
it  yields  p-iodo-o-acetotoluidide.  M.P.  167.5°. 

p-Chloromercuri-o-acetotoluidide. 

The  corresponding  chloromercuri-o-toluidine  is  boiled  with  acetic 
anhydride.  On  cooling  crystals  separate  which  are  easily  soluble  in 
absolute  alcohol.  (Hg).  M.P.  167°. 

o,  p-Diacetoxymercuri-o-acetotoluidide. 

The  diacetoxymercuri  compound  of  o-toluidine  is  treated  with  ethyl 
acetate  and  acetic  anhydride.  Fine  crystals  separate  which  are  in- 
soluble in  common  solvents,  fairly  soluble  in  hot  water,  very  soluble 
in  dilute  acids,  ammonium  hydroxide  and  amines.  (CHNHg).  M.P. 
about  235°.  Treatment  with  iodine  gives  a  diiodide  of  the  formula 
C9H9ONI2,  melting  at  217.5°  (corr.  222.5°). 

Dichloromercuri-o-acetotoluidide. 

The  diacetate  is  treated  with  a  chloride  solution.  (ClHg).  The 
bromide  and  iodide  have  also  been  prepared. 

Derivatives  of  m-Acetotoluidide*20 

Acetoxymercuri-m-acetotoluidide. 

The  toluidide  is  refluxed  with  less  than  one  molecule  of  mercuric 
acetate  in  water.  No  mercuric  ions  are  left  after  one  hour.  Yield  20 
per  cent.  The  product  is  purified  by  recrystallization  from  30  per 
cent  alcohol.  (CHHg).  M.P.  99°.  The  original  mother  liquor  when 
treated  with  a  chloride  solution  gives  a  precipitate  of  the  corresponding 
chloride. 

Diacetoxymercuri-m-acetotoluidide. 

The  corresponding  diacetoxymercuri-m-toluidine  is  treated  with 
acetic  anhydride.  It  is  insoluble  in  common  solvents,  slightly  soluble 
in  hot  water,  very  soluble  in  ammonium  hydroxide.  (Hg).  When 
treated  with  iodine  it  forms  diiodo-m-acetotoluidide  melting  at  209° 
(corr.  214°). 

120  Schoeller,  Schrauth,  and  Rother,  loc.  cit.  2814. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     247 

Triacetoxymercuri-m-acetotoluidide. 

The  corresponding  trimercurated  m-toluidine  is  heated  with  acetic 
anhydride.  The  product  is  insoluble  in  organic  solvents,  soluble  in 
ammonium  hydroxide,  and  very  soluble  in  water  even  in  the  cold. 
(CHHg).  Ammonium  sulfide  gives  no  action  until  boiled. 

Derivatives  of  p-Acetotoluidide. 

Anhydride  of  o-hydroxymercuri-p-acetotoluidide, 

N  — COCH, 

/ 

CH3.C6H3 
\ 
Hg 

The  toluidide  is  boiled  with  aqueous  mercuric  acetate.  The  product 
forms  leaflets.  (Hg).  M.P.  224°  (corr.  229°).  The  loss  of  acetic  acid 
between  the  acetamino  group  and  the  ortho  hydroxymercuri  group 
apparently  takes  place  only  on  boiling.  None  of  the  analogous  de- 
rivatives of  o-  and  m-acetotoluidide  show  this  loss  of  acetic  acid.  It 
happens  that  none  of  these  compounds  having  these  groups  in  the  ortho 
position  is  made  in  boiling  water  solution.  In  each  case  the  prepara- 
tion has  been  from  the  mercurated  toluidine  and  acetic  anhydride. 

Mercury  Derivatives  of  the  Toluidoacetic  Acids. 

o'(?)-acetoxymercuri-o-tolylglycine  ethyl  ester, 

AcOHg  —  C6H3(CH3)  —  NH.CH2C02C2H5. 

Equal  molecules  of  the  toluido  ester  and  mercuric  acetate  are  al- 
lowed to  react  in  methyl  alcohol.  Yield  77  per  cent.  The  product 
is  soluble  in  methyl  and  ethyl  alcohols,  ethyl  acetate,  chloroform,  ace- 
tone, insoluble  in  low  boiling  ligroin.  It  is  soluble  in  ammonium  hy- 
droxide and  in  dilute  acids.  It  is  best  recrystallized  from  ethyl  ace- 
tate. (CHHg).  M.P.  122°.  Saponification  and  acidification  give  the 
anhydride. 

Anhydride  of  o'(?)-hydroxymercuri-o-tolylglycine, 

Hg  — 0 
/  \ 

CH3  — C6H3  C  =  0. 

\  / 

NH  —  CH, 


248  COMPOUNDS  OF  MERCURY 

The  ester  is  warmed  with  2  molecules  of  sodium  hydroxide,  cooled, 
and  treated  with  1  equivalent  of  normal  sulfurie  acid.  Yield  93  per 
cent.  The  anhydride  is  insoluble  in  water  and  organic  solvents  but  dis- 
solves readily  in  alkalies.  (CHHg) . 

Diacetoxymercuri-o-tolylglycine  ethyl  ester. 

The  toluido  ester  is  treated  with  two  molecules  of  mercuric  acetate 
in  methyl  alcohol.  Yield  83  per  cent.  It  is  insoluble  in  ethyl  acetate, 
difficultly  soluble  in  hot  alcohol,  very  soluble  in  ammonium  hydroxide, 
and  saponified  by  hot  alkalies.  (CHHg).  M.P.  164°  (corr.  167°). 

o(?)-acetoxymercuri-m-tolylglycine  ethyl  ester. 

Equivalent  amounts  of  the  toluido  ester  and  mercuric  acetate  are 
allowed  to  react  in  dilute  methyl  alcohol.  Yield  63  per  cent.  It  is 
purified  by  dissolving  in  ethyl  acetate  and  precipitating  by  low  boil- 
ing ligroin.  (CHHg).  M.P.  127°.  Saponification  and  acidification 
yield  a  yellow  anhydride.  (CHHg). 

Triacetoxymercuri-m-tolylglycine  ethyl  ester. 

m-Toluidoacetic  ethyl  ester  is  treated  with  three  molecules  of  mer- 
curic acetate  in  methyl  alcohol.  Yield  20  per  cent.  The  rest  of  the 
material  can  be  recovered  from  the  mother  liquors  as  the  less  soluble 
chloride.  The  acetate  is  difficultly  soluble  in  methyl  and  ethyl  alco- 
hols, easily  soluble  ir*  ammonium  hydroxide,  insoluble  in  most  com- 
mon solvents.  (CHHg).  M.P.  about  182°.  No  di-mercurated  com- 
pound can  be  obtained  from  m-toluidoacetic  ester  in  methyl  alcohol. 
When  only  two  molecules  of  mercuric  acetate  are  used  the  product  is 
an  oily  substance  which  may  be  a  mixture  of  mono-  and  di-mercu- 
rated esters. 

o-Acetoxymercuri-p-tolylglycine  ethyl  ester. 

The  preparation  in  the  usual  way  gives  an  80  per- cent  yield.  The 
properties  of  the  product  resemble  those  of  the  corresponding  mono- 
mercury  derivatives  of  the  o-  and  m-toluidoacetic  esters.  (CHHg). 
M.P.  139°.  Saponification  and  acidification  gives  the  anhydride  which 
forms  a  white  amorphous  precipitate.  (CHHg). 

p-Bromoaniline  reacts  with  mercuric  acetate  giving  a  series  of  com- 
plex mercury  compounds  similar  to  those  obtained  from  p-amino- 
benzoic  ester.121 

121  Unpublished  results,  Whitmore  and  V.  E.  Meharg.  Cf.  Schoeller,  Schrauth,  and 
Liese,  Ber.  52  (1919),  1782. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     249 


Mercury  Derivatives  of  Benzylamine.122 

Benzylamine  and  related  compounds  give  two  types  of  mercury 
compounds  neither  of  which  contains  the  C  —  Hg  linkage.  The  first 
type  consists  of  " addition  compounds"  made  up  of  one  molecule  of  the 
mercuric  salt  and  one  molecule  of  the  amine.  Such  compounds  are 
obtained  from  benzylamine,  benzyl  methyl  amine,  and  benzyl  ethyl 
amine.  Conductivity  measurements  indicate  that  these  are  pentava- 
lent  nitrogen  derivatives  like  C6H5CH2  —  NH2C1  —  HgCl.  The  sec- 
ond type  of  compound  may  be  obtained  by  boiling  the  mercuric  salt 
with  an  excess  of  the  amine.  C6H5CH2  —  NH  —  HgCl  and  the  cor- 
responding acetate  have  been  described.  (CHNClHg).  The  existence 
of  such  a  compound  is  of  interest  in  supporting  Franklin's  theory 
of  ammonobasic  salts. 

Mercury  Derivatives  of  Benzylaniline.123 

p-Benzylaminophenylmer curie  acetate, 

C6H5CH2  —  NHC6H4  —  HgOAc. 

Equivalent  amounts  of  benzylaniline  and  mercuric  acetate  in  50 
per  cent  alcohol  are  allowed  to  react  at  50°.  The  product  is  crystal- 
lized from  hot  benzene.  It  forms  tufted  needles  which  are  insoluble 
in  water,  slightly  soluble  in  cold  alcohol,  fairly  soluble  hot,  easily  solu- 
ble in  chloroform.  (CHHg).  M.P.  144°. 

p-Benzylaminophenylmer  curie  hydroxide. 

The  powdered  acetate  is  treated  with  concentrated  potassium  hy- 
droxide forming  a  crystalline  powder  made  up  of  small  colorless  prisms. 
It  is  slightly  alkaline  to  "sunflower  extract"  but  not  to  phenolphthalein. 
It  dissolves  slightly  in  hot  water  with  decomposition.  It  is  decom- 
posed by  benzene,  and  methyl  and  ethyl  alcohols.  It  starts  to  soften 
at  82.5°  and  melts  at  215°  with  decomposition.  It  contains  1.5  mole- 
cules of  water  of  crystallization.  (Hg,H20). 

The  hydroxide  heated  with  sodium  thiosulf ate  solution  forms  p-mer- 
curibis-benzylaniline. 

1MAndr6,  Compt.  rend.  112  (1891),  997.  Pesci,  Gazz.  cMm.  ital.  26  II  (1896),  54. 
Chem.  Zentr.  1896  II  630.  Z.  anorg.'Chem.  15  (1897),  221.  Prussia,  Gazz.  chim.  ital. 
27  I  (1897), '15.  Franklin,  J.  Am.  Chem.  Soc.  29  (1907),  43.  Ray  and  Dhar,  J.  Chem. 
Soc.  103  (1913),  4. 

123  Prussia,  loc.  cit.     Pesci,  loc.  cit. 


250  COMPOUNDS  OF  MERCURY 

p-Benzylaminophenylmer curie  chloride. 

The  acetate  is  treated  with  calcium  chloride  in  alcohol.  It  forms  a 
white  crystalline  powder  which  is  slightly  soluble  in  hot  benzene,  solu- 
ble in  hot  methyl  and  ethyl  alcohols,  insoluble  in  water.  (Hg).  M.P. 
173-4°.  The  corresponding  nitrate  is  prepared  from  the  hydroxide 
and  a  very  slight  excess  of  20  per  cent  nitric  acid.  It  forms  a  white 
crystalline  powder  which  is  decomposed  by  hot  water  and  is  insoluble 
in  methyl  and  ethyl  alcohols,  slightly  soluble  hot,  insoluble  in  ben- 
zene. (Hg).  M.P.  150°  decomp. 

p-Mercuribis-benzylaniline,  Hg(C6H4  —  NH  —  CH2  —  C6H5) 2. 

A  suspension  of  the  hydroxide  in  water  is  treated  with  an  excess 
of  25  per  cent  sodium  thiosulfate  solution.  The  product  crystallizes 
from  hot  benzene  in  small  colorless  needles.  It  is  insoluble  in  methyl 
and  ethyl  alcohols.  (Hg,  low) .  M.P.  171.5°  with  partial  decomposition. 
During  its  formation  one  equivalent  of  sodium  hydroxide  is  formed  for 
each  molecule  of  the  complex  hydroxide  used. 

Mercury  Derivatives  of  Miscellaneous  Aromatic  Amines. 

The  xylidines  react  with  mercuric  acetate.124 

Various  aminoarylsulfonic  acids  have  been  treated  with  mercuric 
salts.125 

Acetoxymercuri  sulfanilic  acid  is  obtained  as  a  white  amorphous 
solid  on  warming  sulfanilic  acid  with  mercuric  acetate  in  water  solu- 
tion.125* It  is  soluble  in  dilute  alkalies  and  acids. 

Aminoarylarsonic  acids  react  with  mercuric  compounds.126 

Mercury  Derivatives  of  the  Naphthylamlnes. 

N-Mercury  Compounds.127 

When  the  acylated  a-naphthylamines  are  treated  with  mercuric 
chloride  and  sodium  carbonate  N  —  Hg  compounds  are  obtained.  The 
formyl  and  acetyl  derivatives  have  been  treated  in  this  way.  The 
product  reacts  with  sodium  thiosulfate,  potassium  iodide,  and  am- 

124  J.  Rother,  Dissert.  Berlin  1911,  p.  58. 

125  D.  R.  P.  281,009.     Chem.  Zentr.  1915  I  73. 
i25a  private  communication,  G.  W.  Raiziss. 

™Chem.  Zentr.  1909  II  1817.  D.  R.  P.  239,557.  Ghent.  Zentr.  1911  II  1398. 
D.  R.  P.  272,289.  Chem.  Zentr.  1914  I  1469. 

«*  Wheeler  and  McFarland,  Am.  Chem.  J.  18  (1896),  547.  Prussia,  Gazz.  chim. 
ital.  28  II  (1898),  127.  Chem.  Zentr.  1898  II  928. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     251 

monium  bromide  in  the  way  N  —  Hg  compounds  usually  do,  forming 
the  original  — NH —  compound  and  a  molecule  of  inorganic  base 
for  each  N  —  Hg  linkage  broken. 

Addition  compounds  of  the  naphthylamines  have  been  obtained  by 
treating  them  with  mercuric  salts  in  alcohol  solution.128 

C-Mercury  Compounds. 

2,  4-Diacetoxymercuri-a-naphthylamine*2g 

No  monomercury  compound  is  obtainable.  A  solution  of  a-naph- 
thylamine  in  alcohol  and  acetic  acid  is  treated  with  one  or  two  mole- 
cules of  mercuric  acetate.  An  intense  yellow  precipitate  is  first 
formed.  This  soon  changes  to  a  mass  of  white  crystals.  Yield  95  per 
cent.  Sodium  hydroxide  gives  a  slight  yellow  color  but  ammonium  sul- 
fide  gives  no  action  even  on  long  standing.  (Hg,  low,  HO  Ac,  high). 
The  C  —  Hg  linkage  is  slightly  split  by  boiling  with  potassium  iodide 
solution.  The  amount  of  potassium  hydroxide  is  only  5  per  cent  of 
what  would  be  formed  by  complete  splitting  of  both  C  —  Hg  link- 
ages. When  the  mercury  compound  is  treated  with  potassium  iodide 
and  then  with  ammonium  sulfide  a  distinct  blackening  is  observed. 
This  is  further  evidence  of  the  splitting  effect  of  potassium  iodide  on 
some  C  —  Hg  linkages. 

1-Acetoxymercuri-fi-naphthylamine. 

Equivalent  amounts  of  (3-naphthylamine  and  mercuric  acetate  are 
mixed  in  acetic  acid.  The  colorless  solution  soon  deposits  colorless 
crystals.  These  are  soluble  in  water  containing  a  trace  of  alkali.  Con- 
centrated alkali  turns  the  compound  yellow  and  ammonium  sulfide 
readily  forms  mercuric  sulfide.  This  is  in  sharp  contrast  to  the  be- 
haviour of  the  dimercurated  alpha  compound.  Halogen  salts  give 
very  little  alkali,  indicating  that  the  splitting  of  the  C  —  Hg  is  com- 
paratively slight.  (Hg,  low,  HOAc,  high). 

Mercury  Derivatives  of  Naphthylamine  Sulfonic  Acids. 

Derivatives  of  Naphthionic  Acid. 

(a-Naphthylamine-4-sulfonic  acid.)  13° 

""Zinin,  J.  prakt.  Chem.  (1)  27  (1842),  148.  Klein,  Ber.  11  (1878),  1743. 
Leeds,  J.  Am.  Chem.  Soc.  3  (1881),  150.  Lacnowicz  and  Bandrowski,  MonaUU.  9 
(1888),  515.  Lachowicz,  Monatsh.  10  (1889),  893. 

12»Brieger  and  Schulemann,  J.  prakt    Chem.  (2)   89  (1914),  141. 

™Il>id.  151  ff. 


252  COMPOUNDS  OF  MERCURY 

2-Acetoxymercwri  naphthionic  acid. 

A  cold  solution  of  the  sodium  salt  of  naphthionic  acid  is  treated 
with  mercuric  acetate  forming  a  fine  white  precipitate.  Boiling  this 
precipitate  gives  a  compound  which  is  soluble  in  acetic  acid.  When 
the  acetic  acid  solution  is  cooled,  colorless  crystals  separate.  These 
are  soluble  in  sodium  hydroxide  with  only  a  little  blackening.  No 
mercuric  oxide  is  formed.  Ammonium  sulfide  does  not  act  at  first 
but  in  a  little  while  gives  mercuric  sulfide.  (Hg) . 

The  structure  given  seems  more  likely  than  that  suggested  by 
Brieger  and  Schulemann  who  regard  the  compound  as  an  internal  salt 
with  the  mercury  attached  to  the  sulfonic  acid  and  a  molecule  of  acetic 
acid  added  to  the  amino  group.131 

Sodium  salt  of  2-Hydroxymercuri  naphthionic  acid. 

The  acetate  is  treated  with  a  large  excess  of  sodium  hydroxide. 
White  needles  of  the  sodium  salt  separate.  (NaHg) .  The  sodium  salt 
does  not  react  with  ammonium  sulfide.  When  it  stands  in  a  vacuum 
over  phosphorus  pentoxide  it  changes  to  a  canary  yellow  compound. 
This  may  be  due  to  the  elimination  of  water  between  the  amino  group 
and  the  ortho  hydroxymercuri  group  giving  an  anhydride  similar  to 
that  obtained  with  mercurated  toluidine. 

No  dimercurated  naphthionic  acid  has  been  obtained.  When  an 
excess  of  mercuric  acetate  is  used  yellow  solutions  are  obtained  which 
give  a  yellow  red  color  with  sodium  hydroxide. 

Derivatives  of  1,  5-Naphthylamine  Sulfonic  Acid. 

Diacetoxymercuri-1,  5-naphthylamine  sulfonic  acid. 

No  monomercurated  product  has  been  obtained.  A  solution  of  the 
sodium  salt  of  the  acid  is  barely  acidified  with  dilute  acetic  acid  and 
a  water  solution  of  two  molecules  of  mercuric  acetate  is  added.  The 
fine  canary  yellow  precipitate  is  soluble  in  hot  acetic  acid.  Sodium 
hydroxide  dissolves  it  without  forming  any  mercuric  oxide.  This 
alkaline  solution  on  standing  deposits  mercurous  oxide.  The  mercury 
compound  gives  no  action  with  ammonium  sulfide.  (Hg,HOAc).  It  is, 
however,  very  sensitive  to  halide  salts.  Potassium  iodide  gives  a 
quantitative  splitting  of  the  C  —  Hg  linkage.  Although  the  mercury 

181  Their  article  (p.  152)  contains  a  typographical  error  as  this  substance  is 
formulated  as  a  derivative  of  /3-naphthylamine. 


MERCURY  COMPOUNDS  OF  AROMATIC  AMINES     253 

compound  alone  does  not  blacken  with  ammonium  sulfide  it  does  so  at 
once  when  sodium  chloride  is  added.  It  is  remarkable  that  the  C  —  Hg 
linkage  in  this  case  is  more  easily  broken  by  sodium  chloride  than  it 
is  by  a  sulfide. 

Derivatives  of  2,  6-Naphthylamine  Sulfonic  Acid. 

Only  a  monomercurated  compound  has  been  obtained.  The  sodium 
salt  reacts  with  mercuric  acetate  in  the  cold,  giving  a  compound  from 
which  sodium  hydroxide  precipitates  mercuric  oxide.  If  the  mixture 
is  heated  a  product  is  obtained  which  does  not  react  with  sodium 
hydroxide  but  does  react  readily  with  ammonium  sulfide.  The  forma- 
tion of  a  monomercurated  product  which  reacts  at  once  with  ammo- 
nium sulfide  is  the  same  as  with  ce-naphthylamine  itself.  The  product 
is  insoluble  in  all  solvents.  The  analyses  for  mercury,  nitrogen,  and 
acetic  acid  indicate  that  the  substance  is  a  mixture  of  several  com- 
pounds, probably  the  acetate  and  the  internal  salts  formed  between 
the  sulfonic  acid  group  and  the  amino  group,  and  between  the  sul- 
fonic  acid  group  and  the  hydroxymercuri  group.  The  mercury  is 
undoubtedly  in  the  alpha  position  next  to  the  amino  group. 

Sodium  salt  of  l-Hydroxymercuri-2,  6-naphthylamine  sulfonic  acid. 

The  above  impure  product  is  treated  with  an  excess  of  sodium  hy- 
droxide. The  product  is  colorless.  It  is  soluble  in  water,  dilute  alco- 
hol, and  dilute  alkalies.  It  contains  one  molecule  of  water  which 
cannot  be  removed  in  a  vacuum  over  phosphorus  pentoxide.  (CHS 
NaHg). 

The  hydroxide  does  not  react  with  ammonium  sulfide.  If,  how- 
ever, it  is  treated  with  diazotized  sulfanilic  acid  the  solution  immedi- 
ately reacts  with  ammonium  sulfide.  This  indicates  that  the  mercury 
has  been  removed  from  the  ring  during  the  coupling  reaction.  As  the 
coupling  normally  takes  place  in  the  alpha  position  next  to  the  amino 
group,  that  is  probably  the  position  occupied  by  the  mercury. 

When  the  monoethyl  and  dimethyl  derivatives  of  2,  6-naphthyl- 
amine sulfonic  acid  are  treated  with  mercuric  acetate  the  latter  is 
reduced.  No  product  is  obtained  which  does  not  act  at  once  with  am- 
monium sulfide. 

2,  4-Naphthylamine  sulfonic  acid  reacts  with  mercuric  acetate  in 
water  solution  forming  a  compound  which  is  believed  to  be  5-acetoxy- 
mercuri-2,  4-naphthylamine  sulfonic  acid.132 

132  Private  communication,  G.   W.  Raizise. 


Chapter  XI. 

Mercury  Derivatives  of  Phenols,  Naphthols,  and  Related 

Compounds. 

Mercury  Derivatives  of  Phenol.1 

The  compounds  formerly  regarded  as  0  —  Hg  compounds  of 
phenols  are  in  reality  C  —  Hg  compounds.  The  former  compounds 
are  apparently  formed  at  first,  but  quickly  change  to  the  more  stable 
form.  Thus  the  mixing  of  solutions  of  potassium  phenolate  and  mer- 
curic chloride  gives  a  brick  red  precipitate  which  soon  turns  yellow 
and  on  standing  48  hours  becomes  entirely  colorless.  The  first  pre- 
cipitate is  perhaps  a  compound  with  the  grouping  0  —  HgCl  while 
the  latter  is  undoubtedly  p-chloromercuri  phenol. 

Mercuric  salts  of  oxygen  acids  react  readily  with  phenol.  The 
reaction  is  complete  in  less  than  half  an  hour  as  shown  by  the 
fact  that  sodium  hydroxide  no  longer  gives  HgO  with  a  sample  of 
the  mixture.  Mercuric  chloride  reacts  with  phenol  only  to  the  extent 
of  2  per  cent  in  four  days.  In  the  presence  of  sodium  acetate  it  reacts 
about  40  per  cent  in  the  same  length  of  time. 

Mercuric  oxide  reacts  with  sodium  phenolate,  giving  a  white  alkali 
insoluble  compound.2  Phenol  treated  with  mercuric  acetate  solution 
gives  a  mixture  of  the  o-  and  p-  monomercurated  compounds  and  the 
o-  p-  di-mercurated  compound.  The  mixture  is  hard  to  separate.  Simi- 
lar products  are  obtained  from  sodium  phenolate  treated  with  an  alco- 
holic solution  of  mercuric  chloride.  The  "hydrargyrum  carbolicum" 
of  the  pharmacists  is  really  a  mixture  of  the  hydroxides  of  these  three 
compounds. 

1  Desesquelle,  Bull.  soc.  chim.  (3)   11  (1894),  266.    Dimroth,  Ber.  31  (1898),  2155; 
32    (1899),  761.      Ghem.  Zentr.   1901   I   451.     Ber.   35    (1902),   2033,   2853.      Hofmann, 
Ber.  38   (1905),  2002. 

2  Dimroth,  Ber.  31   (1898),  2155. 

254 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      255 

o-Chloromercuriphenol* 
Preparation  and  Properties. 

The  ortho  compound  is  obtained  from  its  mixture  with  the  para 
or  with  the  p-  and  o,  p-  compounds  by  extraction  with  cold  alcohol  in 
which  the  others  are  practically  insoluble.  The  mixture  of  the  chlo- 
rides may  be  obtained  in  two  ways.  Mercuric  acetate  reacts  even  with 
a  large  excess  of  phenol  giving  all  three  products.  If  the  reaction  be- 
tween mercuric  acetate  and  an  excess  of  phenol  is  carried  out  by  heat- 
ing without  a  solvent  the  product  consists  of  a  mixture  of  the  two 
monomercurated  phenols.4  The  o-chloride  can  be  crystallized  from 
hot  water.  M.P.  152.5°  (CHHg).  It  is  soluble  in  sodium  hydroxide. 
The  treatment  of  this  solution  with  alcohol  precipitates  a  crystalline 
sodium  salt. 

Reactions. 

1.  Benzoylation  by  the  Schotten-Baumann  reaction  gives  a  com- 
pound, ClHg  —  C6H4OCOC6H5,  which  crystallizes  from  much  alco- 
hol in  fine  needles.    M.P.  204°  (CHHg). 

Gentle  warming  with  acetyl  chloride  gives  an  80  per  cent,  yield  of 
an  acetyl  derivative  melting  at  170-1°  (Hg).5 

2.  Acid  reducing  agents,  like  dilute  stannous  chloride,  give  metal- 
lic mercury  and  phenol. 

3.  Dilute  acids  readily  split  the  C  —  Hg  bond,  giving  mercuric 
salts  and  phenol. 

4.  Alkylation  of  the  sodium  derivative  by  ethyl  iodide  gives  a 
mixture  of  o-phenetylmercuric  iodide  and  a  considerable  amount  of 
mercury  diphenetyl.    The  formation  of  the  latter  is  probably  due  to 
the  effect  of  the  inorganic  iodide  formed  in  the  reaction.6 

5.  Coupling  with  diazonium  salt  solutions.7 

An  alkaline  solution  of  the  mercurated  phenol  reacts  with  benzene 
diazonium  chloride  solution  giving  p-benzeneazo-o-chloromercuri- 
phenol.  This  forms  a  yellow  hydrate  which  melts  at  about  125°.  The 
dehydrated  substance  is  red  and  melts  at  147°.  The  anhydrous  sub- 
stance prepared  in  a  vacuum  is  very  hygroscopic  while  that  prepared 
at  a  high  temperature  is  not.  The  substance  forms  a  compound  with 

•Dimroth,  Bar.  31   (1898),  2155;  32  (1899),  762.     Chem.  Zentr.  1901  I  451. 
'Whitmore  and  Middleton,  J.  Am.  Chem.  8oc.  43   (1921),  622. 


'Dimroth,  Ber.  32  (1899),  763. 

T  Dimroth,   Chem.  Zentr.   1901   I   451.     Ber.   35    (1902),   2853.      Reitzenstein   and 
Bonitsch,  ,7.  prakt.  Chem.  (2)   86  (1912),  80. 


256  COMPOUNDS  OF  MERCURY 

one  molecule  of  acetic  acid.  (NClHg,HOAc).  It  also  gives  an  addition 
compound  with  one  molecule  of  hydrochloric  acid.  This  molecule  of 
acid  is  lost  only  on  boiling  with  water. 

An  alkaline  solution  of  the  phenol  can  also  be  coupled  with  the 
diazonium  product  from  m-amino  leucomalachite  green.  The  product 
is  a  dark  green  precipitate  which  turns  dark  brown  on  drying. 

6.  Reaction  with  nitrous  acid.    p-Nitroso-chloromercuriphenol.8 
An  alkaline  solution  of  the  o-mercurated  phenol  is  treated  with  so- 
dium nitrite  and  acidified  with  sulfuric  acid  at  — 5°.    The  product  re- 
crystallizes  from  xylene  or  anisole  in  light  brown  needles.   (NCI) .  It  is 
partly  soluble  in  ether  with  a  green  color.    It  reacts  with  a  mixture 
of  ammonium  chloride,  acetate,  and  carbonate  forming  p-nitroso-o- 
chloromercuri  aniline. 

7.  An  alkaline  solution  of  the  anhydride  of  o-hydroxymercuri 
phenol  when  treated  with  carbon  dioxide  gives  a  precipitate  of  an  inner 
anhydride  of  o-hydroxymercuriphenol.     This  is  insoluble  in  all  or- 
ganic solvents  except  phenol.    (CHHg,MW  in  phenol).9 

Similar  compounds  have  been  observed  in  other  cases  where  the 
—  HgOAc  group  is  ortho  to  the  —  OH  group,  as  in  the  case  of  Tri- 
acetoxymercuriphenolphthalein  which  loses  acetic  acid  at  120°  forming 
such  an  anhydride.10 

8.  With  inorganic  halides.11 

Boiling  with  an  excess  of  aqueous  potassium  iodide  gives  phenol, 
inorganic  mercury  compounds,  and  almost  exactly  one  molecule  of 
alkali.  This  easy  splitting  of  the  C  —  Hg  linkage  in  the  mercurated 
phenol  is  in  sharp  contrast  to  the  behaviour  of  the  corresponding  acety- 
lated  compound  which  reacts  with  potassium  iodide  giving  the  R2Hg 
compound,  mercury  di(o-acetoxyphenyl),  (CH3CO  —  OC6H4)2Hg. 

9.  With  potassium  sulfocyanate.12 

Boiling  with  potassium  sulfocyanate  gives  an  alkaline  solution  and 
a  strong  odor  of  phenol.  Apparently  potassium  sulfocyanate  has  the 
same  splitting  effect  on  the  C  —  Hg  linkage  as  potassium  iodide.  The 
similarity  of  the  action  of  the  two  reagents  is  complete  as  the  sulfo- 
cyanate also  reacts  with  the  acetylated  compound  giving  mercury 
di  (o-acetoxyphenyl) . 

•Kharasch  and  Piccard,  J.  Am.  Chem.  Soc.  42  (1920),  1860. 

•D.  R.  P.  272,607.     Frankel,  671.     Brit.  Pat  24,981.     Chem.  Abst.  6  (1912),  1547. 

10  White,  J.  Am.  Chem.  Soc.  42  (1920),  2363. 

11  Whitmorc  and  Middleton,  loc.  cit. 

12  Unpublished  results,  Whitmore  and  Middleton. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      257 

p-Acetoxymercuri  phenol.13 

Mercuric  chloride  acting  on  eight  moles  of  potassium  phenolate 
gives  a  precipitate  which  was  formerly  regarded  as  basic  mercuric 
phenolate  but  is  probably  a  C  —  Hg  compound.  When  this  is  treated 
with  acetic  acid,  colorless  prisms  are  obtained  which  melt  with  de- 
composition at  a  high  temperature.  The  substance  is  very  little  solu- 
ble in  water  and  alcohol.  (HgCH) . 

A  compound  which  may  be  the  same  as  that  just  mentioned  is 
obtained  by  adding  more  mercuric  acetate  to  the  precipitate  obtained 
from  the  sodium  phenolate  and  mercuric  acetate.  It  is  described  as 
consisting  of  crystals  melting  at  149°. 

p-Chloromercuriphenol.141 
Preparation  and  Properties. 

1.  From   the   mother   liquor   from   the   di-acetoxymercuriphenol 
treated   with   sodium   chloride   solution.     The    resulting    precipitate 
is   extracted  with   cold  alcohol  to  remove  any   of  the  ortho  chlo- 
ride. 

2.  The  mixture  of  the  ortho  and  para  acetates,  obtained  by  fusing 
mercuric  acetate  with  an  excess  of  phenol,  is  dissolved  in  hot  alcohol 
and  precipitated  by  sodium  chloride  solution.    The  p-chloride  precipi- 
tates even  hot  and  is  filtered  off  at  once  leaving  the  ortho  compound 
in  the  mother  liquor.15     It  is  recrystallized  from  acetone  or  alcohol. 
Fine  needles.     M.P.  219-220°    (224-5°)    (CHHg).     It  is  soluble  in 
alkali. 

3.  Five  per  cent  phenol  solution  in  water  is  heated  with  alum, 
zinc  sulfate,  and  mercuric  chloride.    The  solution  on  standing  deposits 
crystals  melting  at  210°. 

4.  A  solution  of  potassium  phenolate  treated  with  mercuric  chlo- 
ride solution  at  35-40°  gives  a  brick  red  precipitate  which  turns  yel- 
low and  then  white  on  standing  for  48  hours.     Extraction  with  hot 
alcohol  gives  colorless  crystals  which  melt  about  210°  with  decompo- 
sition.    (CHClHg). 

18  Desesquelle,  Bull.  soc.  cMm.  (3)  11  (1894),  268. 

"  Desesquelle,  loc.  cit.  Dimroth,  Ber.  31  (1898),  2155;  32  (1899),  761.  Grutzner, 
Arch.  Pharm.  236  (1899),  622.  Chem.  Zentr.  1899  I  203.  Dimroth,  Chem.  Zentr. 
1901  I  452.  Ber.  35  (1902),  2862.  Brit.  Pat.  24,981.  Chem.  Abst.  6  (1912),  1547, 

»•  Whitmore  and  Middletoo,  loc,  cit 


258  COMPOUNDS  OF  MERCURY 

Reactions. 

1.  The  Schotten-Baumann  reaction   gives   a   benzoyl  derivative 
which    crystallizes    from    ethyl    benzoate   in    leaflets.      M.P.    275-6° 
(CHHg).16 

Treatment  with  acetyl  chloride  gives  an  acetyl  derivative  which 
melts  at  235°  (Hg).17 

2.  With  diazonium  salts.18 

An  alkaline  solution  of  the  chloride  reacts  with  benzene  diazonium 
chloride  forming  hydroxyazobenzene,  mercuric  oxide,  and  a  small 
amount  of  o-benzeneazo-p-chloromercuriphenol.  The  latter  substance 
forms  yellow  masses  containing  acetic  acid.  Dried  at  100°  it  turns 
red.  M.P.  130-1°  (CHHg).  Most  of  the  mercury  in  the  position 
in  which  coupling  usually  takes  place  is  split  out  as  inorganic  mer- 
cury. 

3.  With  inorganic  halides.19 

Boiling  with  potassium  iodide  solution  removes  the  mercury  quan- 
titatively forming  phenol,  potassium  hydroxide,  and  potassium  mer- 
curic iodide.  The  corresponding  acetylated  compound  does  not  lose 
mercury  when  treated  in  this  way  but  is  only  changed  to  the  organo- 
mercuric  iodide,  CH3CO  —  OC6H4HgI. 

Miscellaneous  work  on  p-chloromercuriphenol.20 

p-Hydroxymercuriphenol.2* 

The  white  precipitate  formed  from  mercuric  chloride  and  an  excess 
of  potassium  phenolate  probably  has  this  structure.  It  can  be  crystal- 
lized from  a  hot  concentrated  phenol  solution.  (HgCH). 

The  oxide  corresponding  to  this  hydroxide,  (HO  —  C6H4 —  Hg)20, 
is  obtained  by  dissolving  the  chloride  in  sodium  hydroxide  and  precipi- 
tating by  carbon  dioxide.  Extraction  with  acetone  removes  impurities. 
It  decomposes  slowly  at  180°.  It  is  insoluble  in  all  organic  solvents 
except  boiling  phenol  from  which  alcohol  causes  it  to  separate  as  a 
crystalline  powder.  Apparently  the  internal  anhydride  cannot  exist  as 
it  does  with  the  corresponding  ortho  compound.22 

"Dimroth,  Ber.  32  (1899),  761. 

17  Whitmore  and  Middleton,  loc.  cit. 

"Dimroth,  Chetn.  Zentr.  1901  I  451.     Ber.  35   (1902),  2853. 

39Whitraore  and  Middleton,  loc.  cit. 

20  Brit.  Pat.  24981  loc.  cit.     Frankel,  Die  Arzneimittelsynthese,  4th  Ed.  1919,  p.  671. 

21  Desesquelle,    loc.    cit.      Realenzyk.    Pharm.    VI    500.      Schmidt,    Pharmazeutische 
Chemie,  II  1076. 

"JDjuiroth,,  Chem.  Zentr.  1901  J  450.     Ber.  35   (1902),  5854, 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      259 

Di-mercurated  Compounds  of  Phenol.23 

Di-acetoxymercuri  phenol. 

An  aqueous  solution  of  phenol  and  two  moles  of  mercuric  acetate 
is  heated  on  the  steam  bath.  M.P.  216-7°  (CHHg). 

Reactions. 

1.  Iodine  reacts  with  the  di-acetate  in  acetic  acid  forming  di- 
iodophenol.    The  action  with  iodine  is  quantitative  and  the  reaction 
can  be  used  as  a  method  of  analyzing  mercurated  phenols  by  iodim- 
etry.24 

2.  With  diazonium  salt  solutions. 

Benzene  diazonium  chloride  reacts  with  the  di-acetate  dissolved 
in  dilute  sodium  hydroxide  giving  p-benzeneazo-o-acetoxymercuri- 
phenol  in  the  alkaline  solution  and  an  insoluble  residue  of  mercuric 
oxide  and  o-benzeneazo-o,  p-diacetoxymercuriphenol.  The  latter  is  ob- 
tained as  the  chloride  by  dissolving  the  residue  with  warm  dilute  so- 
dium hydroxide,  precipitating  by  carbon  dioxide,  dissolving  in  acetic 
acid  and  precipitating  by  sodium  chloride. 

3.  With  inorganic  halides.25 

Boiling  with  aqueous  potassium  iodide  splits  the  C  —  Hg  linkage 
quantitatively  giving  phenol,  potassium  mercuric  iodide,  and  almost 
exactly  two  equivalents  of  base. 

p-Benzeneazo-o-acetoxymercuri-phenol.  Yellow  powder.  M.P.  197-8° 
(CHHg). 

Sodium  chloride  gives  the  corresponding  chloride.  o-Benzeneazo-o, 
p-dichloromercuriphenol  precipitated  by  sodium  chloride  from  acetic 
acid  solution  contains  one  molecule  of  acetic  acid.  It  forms  a  red 
brown  powder.  M.P.  165-70°  decomp.  It  loses  acetic  acid  at  110°  or 
on  boiling  with  water.  (CHHg,HOAc) . 

The  sodium  salt  of  o,  p-dihydroxymercuriphenol  is  known  as  "Pro- 
vidol." 26 

o,  p-Dichloromercuriphenol.27 

If  the  product  from  the  mercuration  of  phenol  in  solution  is  treated 
with  sodium  chloride  and  the  resulting  precipitate  is  extracted  with 

23Dimroth,  Ber.  31  (1898),  2154;  32  (1899),  763;  35  (1902),  2863.  Chem.  Zentr. 
1901  I  452.  Brieger,  Arch.  Pharm.  250  (1912),  62.  Chem.  Zentr.  1912  I  753.  Brit. 
Pat.  24,981  loc.  cit. 

"Brieger,  loc.  cit. 

25  Whitmore  and  Middleton,  loc.  cit. 

26  Frankel,  loc.  cit.  659. 
"Dimroth,  Ber.  32  (1899),  763. 


260  .         COMPOUNDS  OF  MERCURY 

boiling  alcohol,  the  residue  is  the  di-chloride  compound.  White  pow- 
der, almost  insoluble  in  all  solvents.  Decomposes  at  258°  without 
melting.  (CHHg).  The  benzoyl  compound  is  prepared  in  the  usual 
way.  It  is  a  white  powder  insoluble  even  in  ethyl  benzoate.  (CH) . 

Mercuribis-phenol  Compounds. 

Mercutibis-o-phenol.28 

If  the  ortho  chloride  is  treated  with  sodium  thiosulfate  a  clear 
solution  is  firstjobtained.  In  a  few  seconds  this  becomes  cloudy.  The 
white  powder  formed  can  be  crystallized  in  small  amounts  from  hot 
alcohol.  The  recrystallization  must  be  carried  out  as  rapidly  as  pos- 
sible to  avoid  decomposition.  The  product  forms  white  tablets, 
rather  easily  soluble  in  alcohol,  acetic  acid,  and  acetone,  almost  in- 
soluble in  water,  ether,  and  chloroform  even  on  boiling.  Heating 
causes  it  to  turn  gray  without  melting.  The  alcohol  solution  on  boil- 
ing for  a  few  minutes  turns  brown  and  deposits  metallic  mercury.  It 
is  easily  soluble  in  sodium  hydroxide,  insoluble  in  sodium  carbonate, 
precipitated  by  carbon  dioxide  from  alkaline  solution.  (CHHg). 

Mercuribis-o-phenylacetate,  Hg(C6H40  —  COCH3)2.29 
Preparation. 

1.  The   acetyl    derivative    of   o-hydroxyphenylmercuric    chloride* 
boiled  with  potassium  iodide  solution  gives  a  20  per  cent  yield  of  R2Hg. 

2.  The  acetyl  derivative  of  o-hydroxyphenylmercuric  chloride  dis- 
solves readily  in  sodium  thiosulfate  solution.    On  standing  three  days 
an  80  per  cent  yield  of  R2Hg  separates. 

Properties. 

It  forms  white  needle  crystals  which  melt  at  125°.  It  is  slightly 
soluble,  on  heating,  in  alcohol,  benzene,  and  chloroform.  It  is  only 
difficultly  soluble  in  ether.  (Hg) . 

Reactions. 

1.    With  inorganic  halides. 

Boiling  with  an  excess  of  potassium  iodide  produces  no  change. 
The  stability  of  the  C  —  Hg  linkage  is  evidently  increased  by  the 
acetylation  of  the  phenolic  hydroxyl. 

28Dimroth,  Ber.  35  (1902),  2855.     Chem.  Zentr.  1901  I  449-54. 
and  Middleton,  J.  Am.  Chem.  Soc.  43  (1921),  619. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      261 

2.  With  mercuric  chloride. 

The  usual  reaction  of  R2Hg  compounds  takes  place  forming  o-ace- 
toxyphenylmercuric  chloride  melting  at  170°. 

3.  With  bases. 

Sodium  hydroxide  not  only  saponifies  the  acetoxy  groups  but  breaks 
one  of  the  C  —  Hg  linkages.  This  change  of  R2Hg  to  RHgX  by 
means  of  a  base  is  very  unusual.30  Boiling  with  5  per  cent  sodium 
hydroxide  and  neutralizing  with  acetic  acid  gives  a  white  amorphous 
substance  which  appears  to  be  (HO  —  C6H4  —  Hg)  20.  (Hg) .  It  is  thus 
analogous  to  the  compound  obtained  in  the  para  series,31  by  dissolving 
RHgCl  in  sodium  hydroxide  and  precipitating  by  carbon  dioxide. 

4.  With  acids. 

Concentrated  hydrochloric  acid  has  little  action  except  on  heating 
or  standing  for  some  time.  This  is  evidenced  by  the  fact  that  a  sus- 
pension of  the  mercury  compound  in  the  acid  does  not  react  with 
hydrogen  sulfide  unless  heated  or  allowed  to  stand  at  least  an  hour. 

5.  With  sulfides. 

No  reaction  takes  place  with  ammonium  sulfide  in  less  than  three 
days.  Then  a  slight  red  precipitate  separates. 

Mercuribis-p-phenylacetate. 

The  preparation  and  properties  of  this  substance  resemble  those  of 
the  ortho  compound.  It  is,  however,  harder  to  bring  about  the  change 
to  R2Hg  than  in  the  ortho  series.  Treatment  of  p-acetoxyphenyl- 
mercuric  chloride  with  an  excess  of  potassium  iodide  produces  no 
change  but  the  formation  of  the  organomercuric  iodide.  No  R2Hg 
can  be  obtained  in  this  way.  The  reaction  with  sodium  thiosulfate 
gives  the  desired  compound.  The  yield  is  only  50  per  cent  as  com- 
pared with  that  of  80  per  cent  obtained  in  the  preparation  of  the  ortho 
compound.  The  product  melts  172-3°.  Its  solubilities  resemble  those 
of  the  ortho  compound.  It  reacts  with  mercuric  chloride,  sodium  hy- 
droxide, acids,  and  sulfides  in  the  same  way  as  its  isomer. 

Reaction  of  Phenol  Ethers  with  Mercuric  Compounds. 

Phenol  ethers  react  much  less  readily  with  mercuric  acetate  than 
do  the  free  phenols.  They  must  be  heated  on  the  water  bath  and 

s°Whitmore  and  Middleton,  ibid.  624.  Stieglitz,  Kharasch,  and  Hanke,  J.  Am. 
Chem.  Soc.  43  (1921),  1185. 

"Dimroth,  Bar.  35  (1902),  2854. 


262  COMPOUNDS  OF  MERCURY 

even  then  only  one  mercury  atom  is  introduced  into  the  ring.32  Man- 
chot  believes  that  an  "addition"  compound  is  formed  first  and  then 
rearranges  in  such  a  way  that  the  mercury  replaces  a  ring  hydrogen. 

Derivatives  of  Anisole. 

o-Mercury  Dianisyl.33 
Preparation. 

1.  From  o-bromanisole  and  1.5  per  cent  sodium  amalgam  in  the 
usual  way. 

2.  From  o-iodomercurianisole  and  sodium  stannite  solution. 

3.  From  o-iodomercurianisole  and  potassium  iodide  solution.34 

Properties  and  Reactions. 

It  crystallizes  in  monoclinic  prisms  which  are  easily  soluble  in 
benzene,  chloroform,  and  less  soluble  in  hot  alcohol.  M.P.  108°.  It 
reacts  with  mercuric  salts  and  with  acids  in  the  usual  way  forming  salts 
of  the  type  R  — Hg  — X. 

o-Acetoxymercuri  anisole. 

Prepared  from  the  dianisyl  compound  dissolved  in  hot  acetic  acid 
and  precipitated  by  water.  When  recrystallized  from  alcohol,  it  forms 
fine  needles.  M.P.  123-4°  (CH). 

o-Halidemercuri  anisoles. 

These  may  be  prepared  by  the  usual  reaction  of  the  R2Hg  com- 
pound with  mercuric  halides  in  alcohol.  They  are  more  soluble  in 
alcohol  than  the  corresponding  p-  compounds.  Chloride.  It  is  also 
prepared  by  adding  sodium  chloride  solution  to  the  mother  liquors 
from  the  preparation  of  the  p-acetate  from  mercuric  acetate  heated 
with  an  excess  of  anisole.35 

When  the  mixture  is  treated  with  steam,  the  o-chloromercuri  com- 
pound passes  over  with  the  unchanged  anisole  leaving  the  p-compound 
behind.  The  chloride  is  crystallized  from  alcohol  in  fine  needles,  from 
chloroform  in  small  tablets.  It  is  difficultly  soluble  in  cold  benzene, 

82Dimroth,  Ber.  35   (1902),  2867.     Manchot,  Ann.  421   (1920),  333. 
8SMichaelis,  Ber.  27   (1894),  257.     Dimroth,  Ber.  35   (1902),  2853. 
84  Unpublished  results,  Whitmore  and  Middleton. 
"Dimroth,  loc.  cit.  2867. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      263 

more  easily  in  hot  benzene  and  chloroform.  M.P.  173-4038  (Cl).  Bro- 
mide M.P.  183°  (Br).  Iodide.  It  can  also  be  prepared  from  the  chlo- 
ride by  treating  with  an  iodide  solution.  It  is  also  formed  when  an 
alkaline  methyl  alcohol  solution  of  o-chloromercuriphenol  is  treated 
with  methyl  iodide.37  Small  colorless  needles.  M.P.  165°  (I).  It 
reacts  with  sodium  stannite  solution  or  potassium  iodide  forming 
o-mercury  dianisyl. 

p-Mercury  Dianisyl.38 

It  can  be  prepared  from  p-bromanisole  and  sodium  amalgam  in  the 
usual  way.  Fine  white  needles.  M.P.  202°.  It  sublimes,  on  careful 
heating,  at  200°.  It  is  fairly  soluble  in  cold  benzene,  easily  in  hot 
benzene,  easily  soluble  in  cold  chloroform,  less  soluble  in  alcohol,  in- 
soluble in  hydrochloric  acid,  but  on  long  heating  gives  anisole  and 
mercuric  chloride.  (CHHg) .  When  heated  with  an  excess  of  pure  phos- 
phorus trichloride  at  about  200°  it  gives  mercuric  chloride  and 
CH30  —  C6H4PC12. 

Reaction  of  Anisole  with  Mercuric  Acetate. 

1.    In  water  solution.39 

Addition  compound  of  anisole  and  mercuric  hydroxide. 

The  reaction  at  50°  is  very  slow.  A  white  precipitate  starts  to  form 
after  several  days.  Even  on  long  standing  the  solution  still  contains 
mercuric  ions.  The  precipitate  is  filtered  off  and  dried  on  a  porous 
plate  in  a  vacuum.  M.P.  170°.  Recrystallization  from  25  per  cent 
acetic  acid  gives  fine  needles  melting  at  173°.  7.8  gm.  of  anisole 
treated  with  three  molecules  of  mercuric  acetate  gives  20  gm.  of  the 
precipitate.  It  gives  no  mercury  reaction  with  sodium  hydroxide,  am- 
monium hydroxide,  or  ammonium  sulfide.  Hot  dilute  HC1  gives  anisole. 
The  precipitate  subjected  to  steam  distillation  gives  no  volatile  prod- 
uct. If  acidified  with  20  per  cent  HC1  and  then  steam  distilled  it  gives 
anisole.  It  is  fairly  soluble  in  hot  water  and  can  be  recrystallized  from 

38  A  chloride  melting  177-8°  is  obtained  in  the  following  manner  :  o-Hydroxyphenyl- 
mercuric  chloride  is  treated  with  sodium  hydroxide  and  methyl  iodide  forming  o-anisyl- 
mercuric  iodide.  This  reacts  with  potassium  iodide  giving  o-mercury  dianisyl,  which  in 
turn  reacts  with  mercuric  chloride  giving  o-anisylmercuric  chloride  melting  at  177-8°. 
Unpublished  results,  Whitmore  and  Middleton. 

»7Dimroth,  Ber.  31  (1898),  2155.     Chem.  Zentr.  1901  I  451. 

38  Michaelis,  Ann.  293  (1896),  248.  Michaelis  and  Rabinerson,  Ber.  23  (1890), 
2343. 

"Manchot,  Ann.  421   (1920),  334. 


264  COMPOUNDS  OF  MERCURY 

dilute  alcohol.  It  is  neutral  to  litmus.  It  contains  no  acetate,  (cacodyl 
test) .  (CHHg) .  Analyses  for  C,  H,  and  Hg  agree  with  the  formula, 
(CH30  —  C6H5.HgOH)OH,  which  is  used  to  indicate  that  only  one 
of  the  OH  groups  is  replaceable  by  acid  radicals.  The  substance  seems 
to  lose  water.  It  might,  therefore,  be  a  true  C  —  Hg  compound  con- 
taining one  molecule  of  water.  This  idea  receives  some  support  from 
the  fact  that  the  hydroxide  readily  reacts  with  sodium  chloride  forming 
the  p-chloromercurianisole  of  M.P.  237°.  There  is  no  doubt  of  the 
structure  of  the  latter  compound  as  it  has  been  made  from  p-mercury 
dianisyl  which  in  turn  can  be  made  from  p-bromanisole. 
2.  Without  solvent.40  When  anisole  is  heated  with  mercuric  acetate 
an  acetoxymercuri  group  is  introduced  into  the  p-position. 

p-Acetoxymercuri  anisole. 

Dry  mercuric  acetate  is  heated  with  8  molecules  of  anisole  on  a  wa- 
ter bath  until  the  reaction  is  complete  (NaOH  test).  Cooling  gives 
crystals  which  can  be  recrystallized  from  alcohol.  M.P.  176.5° 
(CHHg) .  The  mother  liquor  treated  with  sodium  chloride  gives  some 
o-compound  which  can  be  removed  by  steam  distillation  along  with 
the  unchanged  anisole. 

The  acetate  can  also  be  prepared  by  dissolving  the  mercury  dianisyl 
compound  in  hot  glacial  acetic  acid  and  cooling  the  solution  to  get 
crystals.  It  is  somewhat  soluble  in  hot  water,  from  which  it  separates 
in  fine  needles.  (CH)  .41 

p-Propionoxymercuri  anisole*2 

p-Mercury  dianisyl  is  dissolved  in  propionic  acid  and  treated  with 
sodium  carbonate  solution  to  neutralize  the  excess  of  acid.'  M.P. 
105.5°. 

p-Halidemercuri  anisoles.43 

These  are  prepared  in  the  usual  way  from  the  R2Hg  compound  and 
mercuric  halides.  Chloride  crystallizes  in  colorless  pearly  leaflets.  It  is 
soluble  in  hot  benzene,  more  soluble  in  chloroform,  difficultly  soluble 
in  alcohol.  M.P.  239°  (Cl).  It  can  also  be  prepared  by  boiling  the 
HgCl2  double  salt  of  antimony  tri-anisyl  with  alcohol.44  When  it  is 

*°Dimroth,  Ber.  35   (1902),  2867. 

41Michaelis  and  Rabinerson,  Ber.  23  (1890),  2345.     Michaelis,  Ber.  27  (1894),  257. 

« IMd.  259. 

"Michaelis  and  Rabinerson,  Ber.  23   (1890),  2344. 

"LSloff,  Ber.  30   (1897),  2836. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      265 

heated  with  arsenic  trichloride  in  a  water  bath  it  forms  anisyl  di- 
chlorarsine  in  good  yield.45  Another  preparation  is  by  adding  sodium 
chloride  to  the  "addition"  compound  of  anisole  and  mercuric  hydroxide 
obtained  from  anisole  and  aqueous  mercuric  acetate  at  50°. 46  Bromide. 
Similar  to  the  chloride.  M.P.  187°  (Br).  Iodide,  colorless  pearly 
leaflets.  M.P.  227°  (I).  The  iodide  is  also  obtained  by  treating 
an  alkaline  alcoholic  solution  of  p-hydroxymercuriphenol  with  methyl 
iodide.47 

Long  boiling  with  potassium  iodide  gives  a  small  amount  of  inor- 
ganic mercury.  The  solution  remains  neutral  indicating  that  there  has 
been  no  splitting  of  the  C — Hg  linkage  and  that  R2Hg  has  been  formed. 
None  of  this  substance  can  be  isolated.  The  only  organic  product  is 
unchanged  iodide.48  This  failure  to  obtain  the  R2Hg  compound  in  the 
para  series  when  it  can  be  obtained  in  the  ortho  series  corresponds  to 
the  results  obtained  with  the  acetylated  ortho  and  para  hydroxyphenyl- 
mercuric  chlorides.49  Apparently  potassium  iodide  causes  the  "coup- 
ling" or  "bridging"  reaction  best  when  the  mercury  is  ortho  to  the 
hydroxyl  group.  This  regularity  probably  holds  true  of  aromatic 
amines.  o-Acetoxymercuri-p-bromodimethylaniline  is  readily  changed 
to  the  R2Hg  compound  by  potassium  iodide.50  On  the  other  hand 
p-acetoxymercuri-dimethylaniline  is  only  changed  to  the  iodide  by 
long  boiling  with  potassium  iodide.51 

The  corresponding  cyanide  and  suljocyanate  are  prepared  in  the 
same  way  as  the  halides.52  Cyanide  M.P.  167.5°.  Sulfocyanate  M.P. 
208°. 

p-Anisylmercuric  oxide,  (CH30  —  C6H4  —  Hg)  20.53 

Prepared  from  a  solution  of  one  of  the  halides  in  hot  sodium  car- 
bonate solution.  Recrystallized  from  alcohol.  M.P.  177°.  It  is  very 
difficultly  soluble  in  water,  easily  soluble  in  alcohol  and  in  hot  sodium 
carbonate  solution.  The  solution  in  water  is  alkaline  but  does  not 
absorb  carbon  dioxide  from  the  air.  (CH). 

"Roeder  and  Blasi,  Ber.  47  (1914),  2752. 

"Manchot,  Ann.  421   (1920),  343. 

"Dimroth,  Ber.  31   (1898),  2155.     Ckem.  Zentr.  1901  I  452. 

"Unpublished  results,  Whitmore  and  Middleton. 

"Whitmore  and  Middleton,  J.  Am.  Chem.  Soc.  43   (1921),  623. 

60  Whitmore,  7.  Am.  Chem.  Soc.  41   (1919),  1850. 

51  Unpublished  results,  Whitmore  and  L.  F.  Howe. 

MMichaelis,  Ber.  27  (1894),  260. 

"Michaelis  and  Rabinerson,  Ber.  23   (1890),  2345. 


266  COMPOUNDS  OF  MERCURY 

Derivatives  of  Phenetole.5* 

o-Mercury  Diphenetyl. 

1.  Prepared  from  the  bromide  and  sodium  amalgam  in  the  usual 
way. 

2.  Obtained  as  a  by-product  in  the  treatment  of  an  alkaline  solu- 
tion of  o-chloromercuriphenol  with  ethyl  iodide.    The  o-iodomercuri- 
phenetole  first  formed  probably  reacts  with  the  inorganic  iodide  pres- 
ent forming  the  R2Hg  compound.    It  forms  shining  needles,  easily  solu- 
ble in  hot  benzene,  xylene,  alcohol,  and  chloroform.     M.P.  83°   (not 
224°).    It  reacts  with  mercuric  salts  and  with  organic  and  inorganic 
acids  giving  the  usual  products. 

3.  o-Phenetylmercuric  iodide  when  refluxed  with  an  excess  of  po- 
tassium iodide  in  dilute  alcohol  gives  a  practically  quantitative  yield 
of  o-mercury  diphenetyl.55 

4.  Potassium  sulfocyanate  gives  the  same  reaction  as  potassium 
iodide  but  the  yield  of  the  mercury  diphenetyl  is  not  as  good.55 

5.  o-Phenetylmercuric  iodide  dissolves  readily  in  concentrated  so- 
dium thiosulfate  solution.     On  standing  o-mercury  diphenetyl  sepa- 
rates.55 

o-Acetoxymercuri  phenetole. 

Prepared  from  the  R2Hg  compound  and  acetic  acid  in  the  usual 
way.  Fine  white  tablets.  M.P.  150.5°  (CH) . 

o-Halidemercuri  phenetoles. 

Prepared  in  the  usual  way  from  the  mercury  diphenetyl  compound 
and  mercuric  halides.  They  are  much  more  soluble  in  alcohol  than  the 
corresponding  para  compounds.  Chloride.  Shining  needles,  easily 
soluble  in  benzene  and  chloroform.  M.P.  132°  (Cl).  Bromide.  If 
dissolved  in  alcohol  and  diluted  with  water,  it  gives  fine  white  needles. 
Recrystallized  from  benzene  or  chloroform,  it  forms  four  sided  shin- 
ing prisms.  M.P.  121°  (Br).  Iodide.  Crystallizes  from  alcohol  in 
thick  prismatic  needles,  from  benzene  in  triangular  prisms.  M.P. 
111.5°.  It  can  also  be  obtained  by  treating  an  alkaline  solution  of 
o-chloromercuriphenol  with  ethyl  iodide.  It  is  obtained  by  adding 
water  to  the  alcoholic  mother  liquors  from  the  R2Hg  compound  which 
is  formed  at  the  same  time. 

"Dimroth,  Ber.  32   (1899),  758.     Michaelis,  Ber.  27   (1894),  261. 
65  Unpublished  results,  Whitmore  and  MMdleton. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      267 

p-Mercury  Diphenetyl.56 

Prepared  in  the  usual  way  from  the  bromide  and  sodium  amalgam. 
It  crystallizes  from  a  concentrated  solution  in  benzene  in  shining  leaf- 
lets. M.P.  135°.  Sp.g.  at  15°  is  1.0028.  Rather  difficultly  soluble  in 
hot  alcohol.  (CHHg).  Hot  concentrated  hydrochloric  acid  readily 
gives  mercuric  chloride  and  phenetole.  It  reacts  with  phosphorus  tri- 
chloride to  form  mercuric  chloride  and  C2H50  —  C6H4  —  PC12. 

The  p-mercury  diphenetyl  cannot  be  prepared  from  p-phenetyl- 
mercuric  iodide  and  potassium  iodide  or  potassium  sulfocyanate  as 
can  the  ortho  compound.  The  reaction  probably  takes  place  to  a  slight 
extent  as  a  small  amount  of  inorganic  mercury  is  formed  but  none  of 
the  "coupled"  compound  can  be  isolated.  The  formation  of  inorganic 
mercury  is  not  due  to  a  breaking  of  the  C  —  Hg  linkage  as  no  alkali 
is  formed.57 

Reaction  of  Phenetole  with  Mercuric  Acetate. 

1.  In  water.58    Addition  compound  of  phenetole  and  mercuric  hy- 
droxide.   The  reaction  is  like  that  of  anisole.    The  white  precipitate 
is  filtered  after  ten  days.    Recrystallized  from  dilute  alcohol  it  forms 
fine  needles  melting  at  135.5°.    It  gives  no  mercury  reactions  with  the 
common  reagents.     It  can  be  recrystallized  from  methyl  alcohol  or 
water.    The  water  solution  reacts  with  potassium  hydroxide  giving  a 
precipitate  which  is  soluble  in  an  excess  of  base.    Warmed  with  dilute 
HC1  it  gives  phenetole.   (CHHg) .  Treated  with  ten  per  cent  potassium 
bromide  solution  it  gives  a  product  melting  at  193°  from  which  can 
be  extracted  p-bromomercuriphenetole  of  M.P.  238°  (Lit.  241.5°). 

2.  Without  solvent.    The  acetoxymercuri  group  is  introduced  into 
the  para  position.59 

p- Acetoxymercuri  phenetole. 

Mercuric  acetate  heated  with  an  excess  of  phenetole  gives  crystals 
which  can  be  recrystallized  from  dilute  acetic  acid  in  tablets.  No 
ortho  compound  is  obtained.  M.P.  162°  (CHHg).  The  acetate  can 
also  be  prepared  from  p-mercury  diphenetyl  and  glacial  acetic  acid.60 

68  Michaelis,  Ber.  27   (1894),  258.     Ann.  293  (1896),  257. 
67  Unpublished  results,  Whitmore  and  Middleton. 
«>Manchot,  Ann.  421  (1920),  334  ff. 

"Dlmroth,  Chem.  Zentr.  1901  I  453.     Ber.  35   (1902),  2867. 
M  Michaelis,  B&r.  27   (1894),  259. 


268"  COMPOUNDS  OF  MERCURY 

Colorless  rhombic  tablets.    Recrystallized  from  alcohol  it  forms  long 
clustered  needles.    (CH)  . 

p-Propionoxymercuri  phenetole.61 

Prepared  by  dissolving  the  R2Hg  compound  in  concentrated  pro- 
pionic  acid  and  pouring  the  solution  into  dilute  sodium  carbonate  so- 
lution. White  powder.  It  crystallizes  from  hot  water  in  fine  white 
silky  needles.  M.P.  116°.  It  is  difficultly  soluble  in  cold  water,  easily 
soluble  hot,  soluble  in  alcohol  and  benzene.  (CH).  The  corresponding 
butyrate  is  made  in  a  similar  way.  Fine  white  needles.  M.P.  129° 
(CH). 

p-Halidemercuri  phenetoles*2 

Prepared  in  the  usual  way  from  mercury  diphenetyl  and  mercuric 
salts  in  alcohol.  Chloride.  Colorless  fine  needles,  rather  difficultly 
soluble  in  alcohol,  easily  soluble  in  hot  benzene  and  chloroform.  M.P. 
234°  (Cl)  .  The  chloride  is  also  obtained  by  boiling  an  alcoholic  solu- 
tion of  the  double  compound  of  mercuric  chloride  and  antimony  tri- 
phenetyl.63  Bromide.  Crystallizes  from  benzene  in  fine  needles,  from 
chloroform  in  shining  leaflets.  Difficultly  soluble  in  alcohol.  M.P. 
241.5°  (Br).  The  bromide  is  obtained  in  an  impure  form  by  adding 
potassium  bromide  to  the  addition  compound  of  phenetole  and  mer- 
curic hydroxide  obtained  from  phenetole  and  mercuric  acetate  in  water 
solution.64  Iodide.  Small  white  needles.  M.P.  216°  (I). 

The  iodide  can  also  be  prepared  by  treating  p-hydroxyphenylmer- 
curic  chloride  with  sodium  hydroxide  and  ethyl  iodide.65 

The  cyanide  and  sulfocyanate  have  been  made  in  the  same  way  as 
the  halides.  The  preparation  of  the  cyanide  from  mercury  diphenetyl 
and  mercuric  cyanide  in  alcohol  requires  heating,  at  120°  in  a  sealed 
tube.  It  forms  fine  large  pearly  leaflets  from  alcohol.  M.P.  158-9°. 
It  is  readily  soluble  in  alcohol,  less  so  in  benzene  and  chloroform.  (N)  . 
The  sulfocyanate  is  prepared  in  the  same  way  as  the  cyanide.  It  is 
crystallized  from  alcohol.  M.P.  210°.  Difficultly  soluble  in  alcohol 
and  benzene. 

«  Michaelis,  Ber.  27  (1894),  259. 


8SL61off,  Ber.  30  (1897),  2842. 

"Manchot,  Ann.  421   (1920),  345. 

85  Unpublished  results,  Whitmore  and  Middleton. 

">  Michaelis,  Ber.  27  (1894),  259. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      269 

Oxide  of  p-mercury  phenetyl,  (C2H50  —  C6H4  —  Hg)  20.66 

It  is  prepared  by  dissolving  one  of  the  halides  in  hot  sodium  car- 
bonate solution  and  cooling.  The  white  powder  is  recrystallized  from 
alcohol  in  fine  white  needles.  M.P.  202°.  It  is  easily  soluble  in  hot 
alcohol,  and  hot  sodium  carbonate  solution  but  difficultly  soluble  in 
water.  (CH). 

Mercury  Derivatives  of  Phenoxyacetic  Acid. 

p  (?)  -Hydroxymercuriphenoxy acetic  acid.67 

The  anhydride  of  this  acid  is  obtained  by  heating  phenoxyacetic 
acid  with  mercuric  oxide  until  the  mixture  is  soluble  in  sodium  hy- 
droxide. The  product  consists  of  white  crystals  insoluble  in  water  and 
common  solvents,  soluble  in  alkalies.  It  is  decomposed  by  heat.  Con- 
centrated HC1  gives  mercuric  chloride.  The  sodium  salt  forms  a  dou- 
ble compound  with  alanine  which  is  soluble  in  water  giving  a  neutral 
stable  solution,  but  is  insoluble  in  alcohol,  ether  and  benzene. 

Similar  mercury  derivatives  have  been  made  from  many  substituted 
phenoxyacetic  acids.68  Among  these  are  the  o-chlorophenol,  thymol, 
guaiacol,  carvacrol,  naphthols,  salicylic  acid,  catechol,  p-cresol,  p- 
xylenol  derivatives  of  acetic  acid,  in  general,  R  —  O  —  CH2C02H.  The 
sodium  salts  of  the  mercury  compounds,  obtained  from  these  aryloxy- 
acetic  acids,  form  stable  water  soluble  compounds  with  alanine  and 
with  sodium  diethylbarbiturate.  The  mercury  compounds  themselves 
are  practically  insoluble  in  all  solvents  and  decompose  on  heating. 

Mercury  Derivatives  of  Substituted  Phenols. 

Derivatives  of  Halogen  Phenols. 

p-Hydroxymercuri-o-chlorophenol.69 

It  is  prepared  by  heating  o-chlorophenol  with  mercuric  oxide  or 
mercuric  salts.  Insoluble  in  water  and  common  solvents,  it  is  soluble 
in  alkalies  and  acids  giving  salts.  It  decomposes  on  heating  and  acts 
with  concentrated  HC1  giving  mercuric  chloride. 

6T  D.  R.  P.  261,229.  Chem.  Zentr.  1913  II  193.  Frankel,  671.  D.  R.  P.  264,267. 
Chem.  Zentr.  1913  II  1183.  Chem.  Abst.  1  (1913)  4046. 

«"  D.  R.  P.  261,229  loc.  cit.  D.  R.  P.  261,875.  Frankel,  670.  D.  R.  P.  264,267 
loc.  cit. 

69  D.  R.  P.  234,851.  Chem.  Zentr.  1911-1  1769.  Chem.  Abst.  8  (1914),  1337. 
Friinkel,  659. 


270  COMPOUNDS  OF  MERCURY 

o-Hydroxymercuri-p-chlorophenol70  Preparation  and  properties 
like  those  of  the  o-chlor  compound.  A  similar  p-bromo  compound  has 
been  prepared. 

o-Acetoxymercuri-p-bromophenol  is  obtained  as  a  pink  solid  by 
treating  p-bromophenol  with  mercuric  acetate  in  warm  water.70a  It 
does  not  dissolve  completely  in  dilute  alkali. 

Mercury  compound  of  tribromophenol.7i 

The  sodium  compound  of  tribromophenol  reacts  with  mercuric  ace- 
tate giving  a  yellow  crystalline  precipitate.  This  is  probably  not  a  true 
organic  mercury  compound  as  it  reacts  with  sodium  hydroxide  forming 
HgO.  Heated  to  110°  it  gives  mercurous  bromide  and  a  gray  insolu- 
ble mercury  compound  which  is  perhaps  related  to  dibromophenol. 
The  original  mercury  compound  is  probably  an  0  —  Hg  compound, 
stable  in  this  case  because  the  o-  and  p-positions  are  occupied. 

Mercury  Derivatives  of  Nitrophenols. 

Nitrophenols  having  a  free  ortho  or  para  position  react  readily 
with  mercuric  oxide  or  mercuric  salts  either  with  or  without  solvents. 
In  the  case  of  picric  acid  the  reaction  is  very  slow  as  only  the  positions 
meta  to  the  hydroxyl  are  open.  Four  types  of  compounds  are  ob- 
tained. The  primary  product  is  usually  the  anhydride  of  the  —  HgOH 
group  and  the  aci-nitro  group.  As  would  be  expected  from  this  quinoid 
structure  these  compounds  are  highly  colored.  If  the  anhydride  is 
treated  with  sodium  hydroxide,  a  colored  sodium  salt  is  obtained.  The 
intense  color  indicates  that  it  is  a  salt  of  the  aci-nitro  quinoid  form 
rather  than  a  sodium  compound  of  the  phenol.  If  the  anhydride  or 
the  sodium  salt  is  treated  with  hydrochloric  acid  a  colorless  chloro- 
mercuri  compound  is  obtained.  If  the  acidification  is  done  with  sul- 
furic  acid,  the  salt  which  would  be  expected  is  apparently  completely 
hydrolyzed  as  a  colorless  hydroxymercuri  compound  is  obtained. 
Anhydride  of  4-hydroxymercuri-2-acinitro  phenol.72 

The  sodium  compound  of  o-nitrophenol  in  alcohol  is  shaken  with 

"Hantzsch  and  Auld,  Ber.  39  (1906),  1117.  D.  R.  P.  234,851.  Chem.  Zentr. 
1911  I  1769.  Frankel,  660. 

TOE  private  communication,  G.  W.  Raiziss. 

^Therap.  Monatsh.  51  (1890),  128.  Hantzsch  and  Auld,  Ber.  39  (1906),  1117. 
Merck,  1907,  p.  282.  Torrey  and  Hunter,  J.  Am.  Chem.  8oc.  33  (1911),  203. 

"Hantzsch  and  Auld,  Ber.  39  (1906),  1115.  D.  R.  P.  234,851.  Chem.  Zentr. 
J911  I  1769.  Frankel,  660.  Schamberg,  Chem.  Abet.  11  (1917),  2247. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      271 

the  calculated  amount  of  mercuric  acetate  in  water.  A  yellow  pre- 
cipitate hard  to  filter  is  obtained.  It  is  insoluble  in  all  solvents.  (CH). 
Ammonium  sulfide  gives  no  action.  Hydrochloric  acid  gives  the  chlo- 
romercuric  compound  and  then  mercuric  chloride.  Iodine  and  bromine 
give  the  iodide  and  bromide  of  o-nitrophenol  of  M.P.'s  89°  and  88° 
respectively. 

4-Hydroxymercuri-2-nitrophenol. 

The  solution  of  the  anhydride  in  sodium  hydroxide  is  treated  with 
dilute  sulfuric  acid.  Pale  yellow  needles.  M.P.  240-50°.  It  is  easily 
soluble  in  acetone,  giving  a  slightly  yellow  solution,  less  soluble  in  alco- 
hol, and  insoluble  in  water.  (Hg) .  . 

Sodium  salt  of  4-hydroxymercuri-2-acinitrophenol. 

It  is  prepared  from  the  anhydride  or  the  chloromercuri  compound 
and  fairly  concentrated  sodium  hydroxide.  Recrystallized  from  dilute 
alcohol  it  forms  deep  red  crystals.73 

4-Acetoxymercuri-2-nitrophenol  is  obtained  as  an  amorphous  solid 
by  heating  together  water  solution  of  o-nitrophenol  and  mercuric  ace- 
tate.7^ 

4-Chloromercuri-8-nitrophenol  is  prepared  from  the  anhydride  and  di- 
lute hydrochloric  acid.  It  is  recrystallized  from  absolute  alcohol  or 
acetone,  forming  pale  yellow  crystals  which  are  soluble  in  ethyl  ace- 
tate, slightly  soluble  in  alcohol  and  ether  and  insoluble  in  chloroform. 
(Hg).  The  solution  in  ethyl  acetate  and  acetone  is  colorless  while 
the  solution  in  pyridine  is  yellow. 

4,  4'-Mercuribis-£-nitrophenol.74: 

The  chloride  or  anhydride  is  reduced  with  the  calculated  amount 
of  a  neutral  or  alkaline  reducing  agent.  Another  preparation  is  by 
heating  an  alkaline  solution  of  m-nitro-p-hydroxy  phenyl  arsenious 
oxide  with  mercuric  chloride.  It  is  recrystallized  from  acetone  or  from 
pyridine  and  alcohol.  It  does  not  melt  at  270°.  It  is  soluble  in  bases. 

Anhydride  of  £-hydroxymercuri-4-acinitrophenol. 

The  preparation  from  the  sodium  compound  of  p-nitrophenol  and 
mercuric  oxide  is  too  slow.  Mercuric  acetate  is  used.  Warming  finally 

73  Schamberg,  loc.  cit. 

73a  private  Communication,  G.  W.  Raiziss. 

7*Launoy  and  Levaditi,  Compt.  rend.  soc.  Uol.  74  (1913),  18.  Cf.  Fourneau  and 
Vila,  J.  pharm.  chim.  (7)  6  (1912),  433.  D.  R,  f».  272,289.  Chem.  Zentr,  1914  J  1469, 
Frankel,  66J. 


272  COMPOUNDS  OF  MERCURY 

gives  a  yellow  powder  which  is  slightly  soluble  in  water,  soluble  in 
pyridine,  but  insoluble  in  other  solvents.  (NHg).  It  does  not  react 
with  potassium  iodide  or  hydrogen  sulfide.  Concentrated  acids  give 
mercuric  salts.  It  forms  a  scarlet  compound  with  one  molecule  of 
pyridine.  It  loses  this  pyridine  at  190°,  giving  the  original  yellow 
compound.  When  the  anhydride  is  treated  with  iodine  it  gives  the 
iodonitrophenol  of  M.P.  152°. 

Sodium  salt  of  @-hydroxymercuri-4-acinitrophenol. 

It  is  prepared  from  the  anhydride  and  sodium  hydroxide  in  the 
form  of  yellow  crystals  containing  one-half  molecule  of  water  of 
crystallization.  It  darkens  on  heating  giving  a  slight  explosion. 
(H20,Na). 

2-Hydroxymercuri-4-nitrophenol. 

It  is  prepared  from  the  sodium  salt  and  a  slight  excess  of  dilute  sul- 
furic  acid  or  from  a  solution  of  the  sodium  salt  treated  with  carbon 
dioxide.  It  forms  an  amorphous  powder.  M.P.  206°.  It  is  soluble 
in  acetone,  alcohol,  and  ethyl  acetate  giving  entirely  colorless  solutions. 
Even  a  pyridine  solution  is  only  slightly  yellow.  (Hg) . 

2-Acetoxymercuri-4-nitrophenol  is  obtained  as  a  yellow  amorphous 
solid  by  warming  p-nitrophenol  with  mercuric  acetate  in  water  solu- 
tion.74a  The  product  is  crystallized  three  times  from  glacial  acetic  acid. 
(HgN) .  It  is  easily  soluble  in  dilute  alkali. 

2-Chloromercuri-4-nitrophenol. 

Prepared  from  the  anhydride  and  hydrochloric  acid.  It  is  recrystal- 
lized  from  alcohol.  M.P.  175°.  Almost  colorless.  It  is  soluble  in  ethyl 
acetate  and  alcohol  giving  colorless  solutions.  (Hg). 

Anhydride  of  2-hydroxymercuri-4-acinitro-6-nitrophenol.'15 

It  is  made  from  freshly  prepared  mercuric  oxide  and  the  calculated 
amount  of  dinitrophenol  boiled  for  16  hours.  The  citron  yellow  pow- 
der is  very  little  soluble  in  water  and  alcohol,  insoluble  in  other  sol- 
vents except  pyridine  with  which  it  forms  a  compound.  The  water 
solution  is  not  precipitated  by  ammonium  sulfide,  potassium  iodide  or 
alkali,  and  is  practically  a  non-conductor.  The  pyridine  compound 
is  precipitated  from  a  pyridine  solution  by  adding  ether.  It  is  a  dark 
yellow  solid,  insoluble  in  common  solvents.  (CH,  pyridine).  It  loses 

7«a  private  communication,  G.  W.  Raiziss. 
"flantjssch  and  Auld,  Ber.  39  (1906),  1105. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      273 

pyridine  on  heating.    The  anhydride  reacts  with  bromine  in  potassium 
bromide  solution  forming  the  bromodinitrophenol  of  M.P.  117°. 

Sodium  salt  of  2-hydroxymercuri-4-acinitro-6-nitrophenol. 

The  chloride  is  treated  with  fairly  concentrated  sodium  hydroxide. 
It  crystallizes  from  dilute  alcohol  in  fine  orange  prisms.  It  explodes 
on  vigorous  heating.  The  crystals  contain  one  molecule  of  water. 
(Na,H20) .  Dilute  HC1  forms  the  chloromercuri  compound  and  dilute 
sulfuric  acid  forms  the  hydroxymercuri  compound. 

2-Hydroxymercuri-4,  6-dinitrophenol. 

The  corresponding  sodium  compound  is  treated  with  dilute  sulfuric 
acid.  The  product  crystallizes  from  absolute  alcohol  as  a  colorless 
microcrystalline  powder.  It  is  slightly  soluble  in  alcohol  and  ethyl 
acetate  giving  colorless  solutions.  It  is  easily  soluble  in  pyridine  with 
a  yellow  color.  (Hg) . 

2-Chloromercuri-4)  6-dinitrophenol. 

It  is  prepared  from  the  anhydride  and  dilute  hydrochloric  acid. 
The  colorless  product  is  recrystallized  from  alcohol  by  adding  water. 
M.P.  182°  decomp.  It  gives  almost  colorless  solutions  in  alcohol 
and  chloroform,  entirely  colorless  in  acetic  acid  and  ethyl  acetate. 
(ClHg).  A  benzoyl  derivative  is  obtained  by  the  Schotten-Baumann 
reaction. 

Mercury  derivatives  of  picric  acid™ 

The  compounds  most  easily  obtained  are  undoubtedly  0  —  Hg 
compounds. 

Anhydride  of  8-hydroxymercuri-4-acinitro-2,  6-dinitrophenol. 

When  the  mercury  picrate  obtained  from  picric  acid  and  mercuric 
oxide  is  boiled  with  water  for  a  few  days  the  solution  becomes  indiffer- 
ent to  hydrogen  sulfide.  The  best  method  of  preparation  is  to  boil  the 
solution  for  only  a  few  hours  and  then  cool  it.  The  C  —  Hg  compound 
separates  first.  Washing  with  alcohol  removes  any  0  —  Hg  compound 
mixed  with  it.  It  forms  small  yellow  crystals  which  decompose  on 
heating.  The  yellow  water  solution  of  the  substance  is  neutral  and 
gives  no  precipitate  with  sodium  hydroxide,  potassium  iodide,  ammo- 
nium sulfide,  and  is  practically  a  non-conductor.  It  is  only  slightly 

nm$.  1110. 


274  COMPOUNDS  OF  MERCURY 

soluble  in  common  solvents.    (HgN).   Dilute  hydrochloric  acid  gives 
the  corresponding  chloromercuri  compound. 
Hydroxymercuri-picric  acid. 

The  sodium  salt  or  the  anhydride  is  treated  with  dilute  sulfuric 
acid.  The  product  is  yellow  at  first  but  gradually  becomes  colorless. 
The  solution  in  alcohol  or  acetone  is  colorless.  It  is  almost  insoluble 
in  water  even  on  boiling.  It  apparently  has  no  aci-  form. 

Sodium  salt  of  3-hydroxymercwri-4-acinitro-2,  6-dinitrophenoL 

It  is  prepared  from  the  chloromercuri  compound  and  sodium  hy- 
droxide. It  decomposes  on  rapid  heating.  (Na) .  It  crystallizes  from 
alcohol  in  beautiful  yellow  needles  which  are  easily  soluble  in  water. 

Chloromercuri-picric  acid. 

The  anhydride  is  treated  with  dilute  hydrochloric  acid.  It  crystal- 
lizes from  chloroform  in  pale  yellow  crystals.  M.P.  118°.  It  is  easily 
soluble  in  alcohol  and  pyridine  giving  a  deep  yellow  color,  difficultly 
soluble  in  chloroform  but  with  a  much  brighter  color.  (Hg) . 

Mercury  Derivatives  of  Amino  Phenols. 
p-Chloromercuri-o-aminophenol.'17 

This  is  the  probable  structure  of  the  product  obtained  by  adding 
sodium  hydroxide  and  mercuric  chloride  to  the  hydrochloride  of  m-am- 
ino-p-hydroxyphenyl  dichlorarsine  and  precipitating  the  resulting  so- 
lution with  acetic  acid. 

4,  4'-Mercuribis-%-aminophenol.78 

Prepared  by  vigorous  reduction  of  the  chloromercuri  or  hydroxy- 
mercuri  compound  of  o-nitrophenol  in  neutral  or  alkaline  solution. 
The  diacetyl  derivative  of  this  substance  has  been  made.79 

Several  mercury  derivatives  of  m-dimethylaminophenol  have  been 
prepared.80  Acetoxymercuri-m-dimethylaminophenol  and  its  acetyl  de- 
rivative have  been  made  and  tested  with  sulfides.  The  former  is  re- 
active and  the  latter  unreactive.  A  remarkable  property  of  this  type 
of  mercury  compound  is  that  the  mercury  diphenyl  derivative  can  be 
prepared  directly  from  mercuric  acetate  and  the  quarternary  am- 
monium acetate  obtained  from  the  amino  phenol.  This  reaction  is 

77  D.  R.  P.  272,289.     Ghent,.  Zentr.  1914  I  1469. 

78  Launoy  and  Levaditi,  loc.  cit.     Fourneau  and  Vila,  loc.  cit. 
"Ohern.  Abet.  7  (1913),  1384. 

80Kharasch  and  Chalkley,  private  communication. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      275 

without  parallel  in  the  chemistry  of  organic  mercury  compounds.  It 
may  be  represented  by  the  equation, 

Hg(OAc)2  +  2HO  — C6H4  — N(CH3)3OAc^ 
2HOAc+  [HO  — C6H3  — N(CH3)3OAc]2Hg. 

p-Oxyphenylethyl  amine  reacts  with  sodium  hydroxide  and  mercuric 
chloride  giving  a  white  precipitate,  C9H10ONHg.81 

4-Acetoxymercuri-3-acetaminophenol  is  obtained  as  a  white  powder 
by  warming  o-acetaminophenol  and  mercuric  acetate  in  water  solu- 
tion.81a  It  is  soluble  in  dilute  alkali. 

2-Acetoxymercuri-4-chloro-6-aminophenol  is  obtained  as  a  yellow 
powder  by  warming  p-chloro-o-aminophenol  with  mercuric  acetate  in 
methyl  alcohol  solution.814  It  is  soluble  in  dilute  alkali. 

Aminophenol  sulfonic  acid  HI  forms  a  compound  on  heating  with  mer- 
curic oxide.82 

p-Chloro-o-nitrophenol  forms  a  compound  when  heated  with  mercuric 
oxide.83 

When  the  chloronitrophenol  is  treated  with  mercuric  acetate  in 
water  or  in  methyl  alcohol  no  organic  mercury  compound  is  obtained.83* 
2-Nitro-5-iodophenol  reacts  with  mercuric  acetate  in  boiling  water 
giving  an  organic  mercury  compound.83* 

6,  6'-Mercuribis-l-hydroxy-2-methyl-benzene-4-arsonic  acid. 

It  is  prepared  by  the  neutral  or  alkaline  reduction  of  the  product 
obtained  by  heating  o-cresol  arsonic  acid  with  mercuric  oxide.84 

Mercury  Derivatives  of  p-Cresol.ss 

p-Cresol  reacts  with  alcoholic  mercuric  acetate  even  more  readily 
than  does  phenol.  At  room  temperature  the  reaction  takes  two  days, 
at  90°  it  is  complete  in  thirty  minutes.  About  equal  amounts  of  the 
mono-  and  di-mercurated  products  are  formed.  The  latter  separates 
almost  pure.  The  mother  liquor  treated  with  sodium  chloride  gives 

81  D.  R.  P.  279,957.     Chem.  Zentr.  1914  II  1334.     FrSnkel,  661. 
sia  private  communication,  G.  W.  Raiziss. 

82  D.  R.  P.  281,009.     Chem.  Zentr.  1915  I  73. 

88  D.  R.  P.  234,851.     Chem.  Zentr.  1911  I  1769.     Frankel,  660. 
838  Private  communication,  G.  W.  Raiziss. 
84  D.  R.  P.  255,030.     Chem.  Zentr.  1913  I  353. 

85Dimroth,   Chem.  Zentr.  1901  I   450.     Ber.  35   (1902),  2856.     J.   Rother,  Dissert. 
Berlin,  1911,  p.  9, 


276  COMPOUNDS  OF  MERCURY 

chloromercuri-p-cresol.     The  diacetoxymercuri-p-cresol  separates  al- 
most pure. 

o-Acetoxymercuri-p-cresol. 

The  anhydride  of  hydroxymercuri-p-cresol  is  heated  with  dilute 
acetic  acid.  Cooling  gives  colorless  leaflets.  Put  in  a  bath  at  150° 
it  melts  at  163°  (CHHg).  When  the  acetate  is  treated  with  potassium 
iodide  no  iodomercuri  compound  is  obtained  but  the  product  is  "de- 
composed." Perhaps  the  C  —  Hg  linkage  is  broken  as  in  the  case  of 
the  mercurated  naphthols  and  phenols.86 

A  sodium  hydroxide  solution  of  the  acetate  reacts  with  benzene 
diazonium  chloride  giving  a  red  precipitate  of  o-benzeneazo-o'-acetoxy- 
mercuri-p-cresol  which  crystallizes  from  acetic  acid  in  red  needles.  It 
darkens  at  262°  and  melts  with  decomposition  at  269°  (CHHgN).  It 
is  difficultly  soluble  in  all  solvents.  Concentrated  hydrochloric  acid 
replaces  the  mercury  by  hydrogen. 

Anhydride  of  o-hydroxymercuri-p-cresol. 

The  chloride  dissolves  in  sodium  hydroxide  giving  a  clear  solution 
from  which  carbon  dioxide  precipitates  the  anhydride.  Another  method 
of  preparation  is  the  treatment  of  an  alcoholic  solution  of  the  chloride 
with  the  calculated  amount  of  boiling  sodium  carbonate.  The  product 
is  a  fine  white  powder,  insoluble  in  water  and  common  solvents.  It 
dissolves  in  hot  phenol  but  gives  poor  crystals.  (CHHg). 

Sodium  compound  of  o-hydroxymercuri-p-cresol. 

The  anhydride  is  dissolved  in  a  very  slight  excess  of  warm  12% 
sodium  hydroxide  free  from  carbonate ;  cooling  the  solution  gives  needle 
crystals  which  turn  yellow  in  light.  (Na) . 

Chloromercuri-p-cresol. 

The  warm  mother  liquor  from  the  diacetoxymercuri  compound  ob- 
tained from  mercuric  acetate  and  p-cresol  is  treated  with  sodium  chlo- 
ride. Fine  needles  separate.  These  are  extracted  with  cold  alcohol 
which  dissolves  the  mono  compound  and  leaves  the  di-.  The  alcoholic 
extract  is  concentrated  and  treated  with  water.  The  substance  is  re- 
crystallized  from  hot  benzene.  (CHHg).  It  is  easily  soluble  in  cold 
alcohol,  very  little  in  cold  benzene,  fairly  soluble  in  boiling  water. 
It  melts  at  166°  forming  a  clear  liquid  which  becomes  cloudy  at  176° 

"Brieger  and  Schulemann,  J.  prakt.  Chem.  (2)   89  (1914),  104. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      277 

and  solidifies  at  183°.  A  benzoyl  derivative  can  be  prepared  by  the 
Schotten-Baumann  reaction.  It  crystallizes  from  benzene  in  very  fine 
needles.  Put  in  a  bath  at  220°  it  melts  at  241-2°  (CHHg).  The 
chloromercuricresol  reacts  with  benzene  diazonium  chloride  giving 
o-benzeneazo-o'-chloromercuri-p-cresol.  This  is  difficultly  soluble  in 
alkali.  It  gives  no  acid  addition  products  like  those  obtained  from  the 
corresponding  phenol  compounds. 

o-Iodomercuri-p-cresol. 

It  cannot  be  made  from  the  chloride  mother  liquors  containing 
acetic  acid  as  mercuric  iodide  splits  out  on  addition  of  potassium  iodide. 
The  pure  chloride  is  treated  with  boiling  water  and  the  calculated 
amount  of  potassium  iodide.  On  cooling  fine  needles  are  formed. 
(CHHgl).  It  turns  yellow  at  145°  and  red  at  170°  but  does  not  melt. 
Part  of  it  sublimes.  It  is  easily  soluble  in  ether  and  alcohol,  difficultly 
in  benzene  and  chloroform,  hardly  soluble  in  ligroin.  It  is  stable  to 
boiling  water  but  is  gradually  decomposed  by  long  boiling  in  alcohol 
or  benzene.  The  iodide  dissolved  in  ether  and  shaken  with  a  slight  ex- 
cess of  iodine  in  potassium  iodide  solution  decolorizes  the  latter.  The 
ether  layer  is  shaken  with  more  potassium  iodide  solution  to  remove 
all  of  the  mercuric  iodide  formed.  The  ether  layer  contains  o-iodo-p- 
cresol. 

Diacetoxymercuri-p-cresol.S7 

This  substance  crystallizes  from  the  reaction  mixture  of  p-cresol 
and  mercuric  acetate.  The  product  is  recrystallized  from  dilute  acetic 
acid  and  air  dried.  It  contains  one  molecule  of  water  of  crystallization. 
This  cannot  be  removed  without  driving  off  acetic  acid  also.  It  de- 
composes at  200°.  The  product  obtained  by  heating  to  drive  off  the 
water  of  crystallization  is  probably  o-hydroxymercuri-o'-acetoxymer- 
curi-p-cresol  or  its  inner  anhydride. 

Derivatives  of  p-Cresol  Methyl  Ether.88 

p-Cresol  methyl  ether  reacts  with  aqueous  mercuric  acetate  giving 
a  crystalline  product  which  gives  analyses  for  carbon,  hydrogen  and 
mercury  which  agree  with  the  formula 

3CH3  —  C6H4OCH3.Hg(OAc)2.2HgO. 

"Brit.  Pat.  24,981.     Chem.  Abst.  6   (1912),  1547. 
MManchot,  Ann.  421   (1920),  337. 


278  COMPOUNDS  OF  MERCURY 

The  substance  is  obtained  by  three  different  methods  of  preparation. 
It  is  recrystallized  from  20%  acetic  acid  or  from  dilute  alcohol.  Am- 
monium sulfide  and  sodium  hydroxide  give  no  mercuric  reactions. 
M.P.  132°. 

o-Chloromercuri-p-cresol  methyl  ether. 

This  substance  is  obtained  by  dissolving  the  above  product  in  dilute 
alcohol  and  adding  hot  10%  sodium  chloride  solution.  The  white 
voluminous  precipitate  crystallizes  from  alcohol  in  white  needles.  M.P. 
162°  (CHHgCl).  It  gives  no  mercury  reactions  with  sodium  hy- 
droxide, ammonium  hydroxide  or  ammonium  sulfide. 

p-Xylenol  reacts  with  a  methyl  alcohol  solution  of  mercuric  acetate 
giving  an  acetoxymercuri  compound.89 

Derivatives  of  Thymol.90 

One  or  two  mercury  atoms  can  be  introduced  into  thymol  depend- 
ing on  the  amount  of  mercuric  acetate  used. 

p(f)-Chloromercuri  thymol. 

Equal  molecules  of  thymol  and  mercuric  acetate  are  boiled  with 
alcohol  containing  a  little  acetic  acid.  On  cooling  a  very  small  amount 
of  the  di-mercurated  product  crystallizes  out.  The  filtrate  is  treated 
with  sodium  chloride  solution  which  precipitates  a  mixture  of  the  mono- 
and  di-compounds.  The  pure  mono  compound  is  obtained  after  sev- 
eral crystallizations  from  40%  alcohol.  It  forms  fine  needles.  M.P. 
139.5°  (CHHg).  It  is  easily  soluble  in  dilute  sodium  hydroxide. 

Diacetoxymercuri  thymol. 

Thymol  is  boiled  with  two  molecules  of  mercuric  acetate  in  alcohol 
containing  a  trace  of  acetic  acid.  The  crystals  which  separate  are  re- 
crystallized  from  a  mixture  of  ethyl  acetate  and  acetic  acid.  (CHHg) . 
Placed  in  a  bath  at  190°  it  melts  at  215-6°.  The  sodium  salt  crystal- 
lizes in  plates  from  a  warm  solution  in  fairly  concentrated  sodium  hy- 
droxide. 

88  D.  R.  P.  250,746.  Chem.  Zentr.  1912  II  1245.  Frankel,  660.  Chem.  Abst.  1 
(1913),  3819. 

wTherap.  Monatsh.  51  (1890),  128.  Dimroth,  Ber.  35  (1902),  2864.  Merck,  1907, 
p.  281. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      279 

Derivatives  of  Phenol  Sulfonic  Acids. 91 

Mercury-p-phenol  sulfonate  in  a  carbonate  solution  does  not  attack 
metal  instruments.  The  compound  of  the  sulfonate  with  ammonium 
tartrate  is  known  as  "Asterol."  92 

An  alkaline  solution  of  phenol  disulfonic  acid  reacts  with  mercuric 
oxide  giving  a  C  —  Hg  compound  which  is  soluble  and  does  not  pre- 
cipitate albumen.93 

Aminophenol  sulfonic  acid  gives  C  —  Hg  compounds.94  Mercury 
sozoiodol  is  not  an  organic  mercury  compound  but  a  mercurous  salt 
of  di-iodo-p-phenol  sulfonic  acid.95 

Mercury  Derivatives  of  Naphthols. 

The  alkali  compounds  of  the  naphthols  react  with  mercuric  solu- 
tions giving  compounds  which  appear  to  be  0  —  Hg  compounds. 
These  often  change  on  standing  from  red  or  yellow  to  white.  This 
color  change  may  indicate  a  change  to  a  C  —  Hg  compound.96 

P_C10H7OHgCl(?)  is  obtained  in  this  way.  (CHClHg).  It  is 
soluble  in  alcohol  especially  on  heating,  very  little  soluble  in  water. 
Alcohol  solution  gives  colorless  prisms  which  gradually  darken.  This 
substance  may  be  a  C  - —  Hg  compound. 

$(C10H7  —  0)JHg.(t).  The  first  precipitate  formed  is  yellow  but 
soon  turns  white.  It  is  insoluble  in  common  solvents  but  dissolves  in 
phenol  or  alcoholic  phenol.  (CHHg). 

(3  —  C10H7  —  OHgOAc(t).  The  above  compound  is  treated  with 
acetic  acid.  (CHHg).  The  product  forms  colorless  crystals,  soluble 
in  alcohol,  very  little  soluble  in  water.97 

4-Acetoxymercuri-a-naphthoL 

It  is  prepared  from  the  naphthol  and  mercuric  acetate  in  acetic 
acid  solution.  The  product  is  precipitated  by  the  addition  of  wa- 
ter.98 If  the  reaction  is  carried  out  in  dilute  acetic  acid  white  crystals 

91  D.  R.  P.  104,904  and  121,656.     Frankel,  674. 
82  D.  R.  P.  157,663.     Frankel,  674. 

93Lumiere,  Compt,  rend.  132   (1901),  145.     Chem.  Zentr.  1901  I  455. 
94  D.  R.  P.  281,009.     Frankel,  670. 
*sChem.  Zentr.  1912  I  1521. 

98  Desesquelle,  Bull.  soc.  chim.   (3)   11   (1894),  264. 

*  Merck,  1-907,  p.  279.  Realenzyk.  Pharm.  VI  491.  Brit.  Pat.  24,981.  Chem. 
AKst.  6  (1912),  1547. 

88  Barnberger,  Bcr.  31   (1898),  2626. 


280  COMPOUNDS  OF  MERCURY 

separate  which  turn  intensely  yellow  on  filtering  and  washing.  Am- 
monium sulfide  does  not  react  at  once.  The  yellow  product  contains 
no  acetate.  The  analyses  for  carbon,  hydrogen  and  mercury  agree 
with  the  assumption  that  the  compound  is  a  hydroxymercuri  naphthol. 
It  is  assumed  to  be  such  a  compound  having  the  mercury  in  the  (3  posi- 
tion. It  is  also  suggested  that  the  color  may  be  due  to  a  quinoid 
structure.  In  this  case  a  molecule  of  water  of  crystallization  would 
have  to  be  assumed.  The  C  —  Hg  linkage  is  split  by  alkali  chlorides, 
bromides  and  iodides  with  increasing  ease  forming  free  alkali. 

2,  4  Diacetoxymercuri-a-naphthol.99 

It  is  prepared  from  the  naphthol  and  the  two  molecules  of  mercuric 
acetate  in  30%  acetic  acid.  It  forms  colorless  needles  which  are  re- 
crystallized  from  acetic  acid.  (Hg,HOAc).  It  is  stable  to  ammonium 
sulfide  but  reacts  with  alkali  halides  the  same  as  the  mono  compound. 

1  -A  ce  toxymercuri-fi-naphthol.1  °° 

Acetic  acid  solutions  of  the  naphthol  and  mercuric  acetate  are 
mixed  in  the  cold.  The  crystalline  precipitate  is  soluble  in  dilute  so- 
dium hydroxide  and  is  precipitated  by  acetic  acid.  (CHHg).  It  forms 
white  shining  needles,  if  rapidly  heated  it  melts  at  185°,  with  blacken- 
ing and  frothing.  It  is  only  slightly  soluble  in  hot  water,  benzene, 
xylene,  ligroin,  ether,  chloroform,  alcohol,  and  acetone.  Soluble  in 
acetic  acid  and  sodium  hydroxide.  The  solution  in  sodium  hydroxide 
gives  a  yellow  precipitate  with  ammonium  sulfide.  This  only  turns 
black  on  heating. 

Beta-naphthol  reacts  with  mercuric  acetate  in  cold  methyl  alcohol 
giving  a  product  which  is  described  as  "5-acetoxymercuri-p-naph- 
thol."  100a  It  is  soluble  in  200  parts  of  ethyl  acetate  and  in  50  parts 
of  a  mixture  of  3  parts  of  toluene  and  1  part  of  95  per  cent  ethyl 
alcohol. 

fi-Naphthol  carboxylic  acid. 

Anhydride  of  l-hydroxymercuri-4-carboxyl-fi-naphthol.101 

Prepared  from  the  naphthol  carboxylic  acid  and  mercuric  acetate. 
The  solution  in  dilute  sodium  hydroxide  reacts  with  diazosulfanilic 

M  Brieger  and  Schulemann,  J.  praJct,  Chem.  (2)   89   (1914),  134. 

100  Bamberger,   loc.    cit.   2624.      Brieger  and   Schulemann,    loc.   cit.    132.     Dimrotb, 
Ber.  32  (1899),  765. 

iooa  private  communication,  G.  W.  Raiziss. 

101  Brieger  and  Schulemann,  J.  prakt.  Chem.   (2)   89  (1914),  180. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      281 

acid  and  urea  forming  the  compound  1-azobenzene  sulfonic  acid-4- 
carboxyl-fi-naphthol.  This  reaction  proves  the  position  of  the  mer- 
cury in  the  original  substance.  A  remarkable  fact  about  this  replace- 
ment of  mercury  is  that  it  takes  place  more  rapidly  than  does  the 
coupling  of  the  diazosulfonic  acid  with  the  unmercurated  naphthol  car- 
boxylic  acids.  The  anhydride  when  treated  with  iodine  in  potassium 
iodide  and  acidified  with  acetic  acid  gives  a  mixture  from  which  can 
be  extracted  ^-iodo-4-carboxyl-(3-naphthol  and  beta  naphthol-4-car- 
boxylic  acid.  The  formation  of  the  latter  is  probably  due  to  the  action 
of  hydriodic  acid  liberated  by  the  action  of  the  acetic  acid  on  the  iodide 
solution. 

Naphthol  sulfonic  acids.102 
2-Acetoxymercuri-l-naphthol-4-sulfonic  acid  sodium  salt. 

It  is  prepared  from  the  impure  sodium  salt  and  mercuric  acetate 
in  water.  It  gives  a  yellow  brown  substance.  Recrystallization  from 
dilute  acetic  acid  gives  a  yellow  brown  substance.  (HgNa).  Sodium 
hydroxide  and  ammonium  sulfide  give  no  reaction.  Halogen  salts 
split  the  C  —  Hg  linkage.  No  di-mercurated  product  could  be  made 
from  this  acid. 

l-Acetoxymercuri-2-naphthol-6-sulfonic  acid  sodium  salt. 

It  is  prepared  by  mercuration  in  water  solution.  White  crystals, 
difficultly  soluble  except  in  presence  of  a  little  sodium  hydroxide  or 
acetic  acid.  (HgNa).  Very  stable  to  ammonium  sulfide,  except  in  the 
presence  of  halide  salts  which  exert  a  "loosening"  effect  on  the  C  —  Hg 
linkage.  Diazo  solutions  couple  with  the  compound  by  replacing  the 
mercury  group.  After  the  reaction  the  mercury  can  be  precipitated 
by  ammonium  sulfide.  No  di-mercury  compound  has  been  obtained.103 
l-Naphthol-5-sulfonic  acid  treated  with  mercuric  acetate  gives  only 
tarry  substances  and  considerable  mercurous  acetate. 
1,  8-Amino  naphthol-4}  6-disulfonic  acid  salts  and  their  benzoyl  and 
dibenzoyl  derivatives  react  with  mercuric  acetate  giving  colored  mer- 
curic compounds.  No  definite  C  —  Hg  compounds  have  been  isolated. 
They  are  apparently  very  unstable. 

1,  8-Amino  naphthol- 4- sulfonic  acid  gives  even  less  stable  mercury 
compounds. 

102  Brieger  and  Schulemann,  ibid.  138  ff. 
108  D.  R.  P.  143,726.     Frankel,  662. 


282  COMPOUNDS  OF  MERCURY 

l-Hydroxymercuri-2-naphthol-8,  6-disulfonic  acic?.104 

The  corresponding  naphthol  compound  is  heated  with  mercuric 
oxide.  Alkaline  or  neutral  reduction  changes  it  to  the  corresponding 
R2Hg  compound. 

1,  8-Dihydroxy-3-6-disulfonic  acid. 

This  substance  gives  yellow  mercury  compounds  which  cannot 
be  isolated  pure.  1,  8-Amino  naphthol-3,  6-disulfonic  acid  gives  very 
unstable  mercury  compounds.  2-Naphthol-3,  6-disulfonic  acid  gives 
mercury  compounds  when  treated  with  alkali  carbonates  and  mercuric 
chloride.105 

Mercury  Compounds  of  Dihydroxybenzenes, 

Pyrocatechol  reduces  mercuric  acetate  to  the  mercurous  com- 
pound.106' m 

3-Mercuri-2-hydroxy-4-/methyl  anisole  compounds  have  been 
made.108 

5-Acetoxymercuri-%-hydroxy-anisole  is  prepared  by  warming  guaiacol 
and  mercuric  acetate  in  methyl  alcohol.  It  is  soluble  in  dilute 
alkali.108a 

Guaiacol  acetate  reacts  with  mercuric  acetate  in  warm  methyl  alco- 
hol giving  a  diacetoxymercuri  guaiacol  acetate  which  is  soluble  in  water 
and  in  dilute  alkalies.  (Hg) .  The  position  of  the  mercury  atoms  has 
not  been  determined.108* 

3-Acetoxymercuri-£-hydroxy-5-nitro-anisole  is  obtained  by  warming 
p-nitroguaiacol  with  a  water  solution  of  mercuric  acetate  on  the  water 
bath  for  about  one  hour.108a  The  product  is  soluble  in  dilute  alkali. 
(Hg,  high). 

p-Nitroguaiacol  acetate  when  warmed  with  mercuric  acetate  in 
methyl  alcohol  gives  a  mercury  compound  which  is  not  completely 
soluble  in  dilute  sodium  hydroxide.180*  The  analysis  for  mercury  comes 
between  the  values  for  one  and  two  atoms  of  mercury. 

M  D.  R.  P.  255,030.     Chem.  Zentr.  1913  I  353. 

05  D.  R.  P.  143,448.     Friinkel,  661. 

06  Leys,  J.  pharm.  chim.   (6)   21    (1905),  388.     Chem.  Zentr.  1905  I  1531. 

07  Brit.  Pat.  24,981.     Chem.  Abst.  6   (1912),  1547. 

08  D.  R.  P.  250,746.     Chem.  Zentr.  1912  II  1245. 
osa  private  communication,  G.  W.  Raiziss. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      283 

Derivatives  of  Resorcinol.109 

The  reaction  between  resorcinol  and  mercuric  acetate  in  water 
solution  is  complete  in  15  minutes.  The  solution  is  filtered  at  once 
into  a  concentrated  sodium  chloride  solution. 

C  hloromercuri-resorcinol. 

The  chloride  mixture  obtained  from  resorcin  is  extracted  with  ether 
which  dissolves  all  but  a  slight  residue.  Most  of  the  ether  is  distilled 
off  and  the  residue  allowed  to  crystallize.  The  mono  compound  is  then 
extracted  from  the  mixture  by  chloroform.  Prisms  containing  chloro- 
form are  obtained.  The  chloroform  compound  melts  at  105°  while  the 
pure  compound  melts  at  123°  and  turns  blood  red  at  170°  (CHClHg). 
It  is  easily  soluble  in  ether.  It  is  difficultly  soluble  in  cold  water, 
soluble  in  warm  water  but  it  soon  changes  to  a  fine  yellow  powder 
which  may  be  the  inner  anhydride  of  the  o-hydroxymercuri  compound. 
The  solution  in  sodium  hydroxide  turns  yellow  and  then  darker,  finally 
giving  a  black  precipitate.  Ammonium  sulfide  gives  HgS  at  once. 

Dichloromercuri-resorcinol. 

Obtained  from  the  residue  insoluble  in  chloroform.  Dissolved  in 
ether  it  gives  a  white  powder  on  evaporation.  It  darkens  about  200° 
without  melting.  (Hg).  It  is  difficultly  soluble  in  alcohol.  Sodium 
hydroxide  decomposes  it  even  more  readily  than  it  does  the  mono  com- 
pound giving  a  black  precipitate. 

6-Acetoxymercuri-2-nitro-resorcin  is  prepared  from  2-nitro-resorcin 
and  mercuric  acetate.109a  (N).  The  corresponding  hydroxymercuri 
compound  is  obtained  from  the  nitroresorcin  and  freshly  precipitated 
mercuric  oxide.  The  chloromercuri  product  is  obtained  from  the  hy- 
droxide by  dilute  hydrochloric  acid.  (NHg) . 

Triacetoxymercuri-phloroglucin.110 

Obtained  from  phloroglucin  and  mercuric  acetate.  Insoluble  in 
water  and  all  common  solvents.  It  is  insoluble  in  solutions  of  sodium 
chloride,  sodium  fluoride,  dilute  sulfuric  acid,  dilute  nitric  acid,  am- 
monium hydroxide  and  potassium  hydroxide,  but  is  soluble  in  hydro- 
chloric acid  and  in  solutions  of  potassium  cyanide,  iodide,  bromide, 

109Dimroth,  Ber.   35    (1902),   2865.      Leys,   J.   pharm.   chim.    (G)    21    (1905),   338. 
Chem.  Zentr.  1905  I  1531.     Merck,  1907,  p.  280.     Realenzyk.  Pharm.  VI  503. 
iwa  private  communication,  O.  W.  Raiziss. 
110  Leys,  loc.  cit 


284  COMPOUNDS  OF  MERCURY 

sodium  thiosulfate,  sodium  sulfite,  and  potassium  sulfocyanate.  This 
compound  is  described  as  an  O  —  Hg  compound  but  it  may  very 
likely  be  a  true  organic  mercury  compound.  The  insolubility  in  alkali 
does  not  necessarily  mean  the  absence  of  free  hydroxyl  groups. 

Allyl  and  Propenyl  Compounds  of  Phenol  Ethers.111 

The  propenyl  compounds  react  with  mercuric  acetate  giving  mer- 
curous  acetate  and  a  glycol,  R  —  CHOH  —  CHOH  —  CH3.  The  allyl 
compounds  give  addition  compounds  containing  basic  mercuric  acetate. 
These  addition  compounds  usually  occur  in  two  isomeric  forms,  one 
crystalline  and  the  other  amorphous  or  syrupy.  One  of  these  forms 
may  be  a  polymer  of  the  other.  If  they  are  formed  by  an  actual 
addition  to  the  double  bond  the  isomers  may  be  of  the  two  types 
R_CH2  — CHOH  — CH2HgOAc  and  R  — CH2  — CH(HgOAc)  - 
CH2OH.  Usually  mercury  adds  to  the  carbon  having  the  most  hy- 
drogen atoms.112  Manchot  believes  that  the  mercurated  products  are 
simply  molecular  compounds  of  the  allyl  compound  and  basic  mer- 
curic salts.113  If  this  theory  is  correct  one  of  the  isomers  may  be  the 
molecular  compound  and  the  other  may  be  the  result  of  a  true  addi- 
tion to  the  double  bond.  The  problem  of  the  structure  of  these  addi- 
tion compounds  is  bound  up  with  that  of  the  mercury  compounds  ob- 
tained from  ethylene  compounds  of  other  kinds.  The  fact  that  all 
of  these  compounds  react  with  acids  giving  the  original  unsaturated 
compounds  throws  doubt  on  their  structure  as  true  compounds  of  the 
type  R  — CHOH  — CH(HgX)  —  R.  Such  a  structure  would  be  ex- 
pected to  give  a  saturated  alcohol,  R  —  CHOH  —  CH2  —  R.  In  the 
case  of  the  mercurated  allyl  compounds  treatment  with  zinc  and  so- 
dium hydroxide  gives  the  original  allyl  compounds  in  the  same  way 
as  do  acids. 

The  difference  in  the  behaviour  of  propenyl  and  allyl  compounds 
to  mercuric  acetate  is  recommended  as  a  means  of  distinguishing  and 
separating  these  types  of  compounds.114  The  propenyl  compounds 
give  an  almost  immediate  precipitate  of  mercurous  acetate  whereas  the 

mBalbiano  and  Paolini,  Ber.  35  (1902),  2994;  36  (1903),  3575.  Balbiano,  Ber. 
42  (1909),  1503.  Manchot,  Ann.  421  (1920),  316.  Balbiano  and  Paolini,  Qazz.  chim. 
ital.  36  I  (1906),  244. 

112  Sand  and  Singer,  Ber.  35   (1902),  3170. 

118  Manchot,  loc.  cit.  316. 

»•  Balbiano  and  Paolini,  Ber.  36  (1903),  3578.     Balbiano,  Ber.  42   (1909),  1503. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      285 

allyl  compounds  give  no  precipitate,  except  in  the  case  of  apiol,  the 
mercury  compound  of  which  is  rather  insoluble.115 

The  propenyl  compounds  which  have  been  found  to  give  glycols 
are  anethole,  isosafrol,  isoeugenol  methyl  ether,  isoapiol,  asarone,  and 
isomyristicine.116 

The  allyl  compounds  which  give  addition  products  containing 
basic  mercuric  acetate  or  its  constituents  are  methyl  chavicol,  safrol, 
eugenol  methyl  ether,  apiol  and  myristicin.117  Of  these,  apiol  gives 
only  one  acetate  and  one  chloride  instead  of  the  usual  pair  of  isomers. 
Perhaps  this  Is  connected  with  the  fact  that  apiol  has  a  group  in  the 
ortho  position  to  the  allyl  group. 

Methyl  chavicol,  p-allyl  anisole.118 

Treatment  with  mercuric  acetate  gives  a  thick  syrup  which  is  ap- 
parently a  mixture  as  it  gives  two  different  chlorides  and  bromides. 
The  acetate  is  soluble  in  sodium  carbonate  and  sodium  hydroxide. 
(CHHg) .  When  the  solution  in  sodium  hydroxide  is  treated  with  zinc 
it  gives  methyl  chavicol  in  50%  yield.  If  the  syrupy  acetate  is  dis- 
solved in  alcohol  and  treated  with  concentrated  potassium  chloride  it 
gives  a  yellow  resin  and  a  solution.119  The  resin  hardens.  When  pow- 
dered it  softens  at  55°  but  gives  no  melting  point.  The  mother  liquor 
on  dilution  deposits  white  needle  crystals'  which  are  almost  insoluble 
in  cold  water  but  are  soluble  in  hot  water  and  alcohol.  M.P.  81-2°. 
Both  the  crystalline  and  amorphous  chlorides  react  with  zinc  and 
sodium  hydroxide  giving  methyl  chavicol.  WThen  an  alcoholic  solu- 
tion of  the  syrupy  acetate  is  refluxed  with  potassium  chloride  a  solu- 
tion results.  On  cooling,  needle  crystals  of  the  chloride  separate. 
M.P.  81-2°  (CHClHg) .  The  mother  liquor  gives  a  resin  which  hardens 
and  can  be  powdered.  Yellow  amorphous.  (ClHg).  Only  a  small 
amount  is  obtained.120  The  acetate  treated  with  potassium  bromide 
gives  a  small  amount  of  an  amorphous  product  and  a  crystalline  com- 
pound melting  at  70-1°,  which  is  soluble  in  hot  water,  alcohol  and 
slightly  in  ether.  (CHBrHg) . 

"'Balbiano  and  Paolini,  loc.  cit.  3582. 

116  Balbiano,  Gazz.  chim,.  ital.  36  I  (1906),  244. 

117  Ibid. 

118Balbiano  and  Paolini,  Ber.  36  (1903),  3580.     Gassz.  chim.  ital.  36  I  (1906),  264. 
Balbiano,  Ber.  42  (1909),  1505. 

"8  Balbiano  and  Paolini,  Ber.  36   (1903),  3580. 
120  Balbiano,  Gasz.  chim.  ital.  36  I   (1906),  266. 


286  COMPOUNDS  OF  MERCURY 

Safrol,  methylene  ether  of  p-allyl  pyrocatechol.121 

The  action  of  mercuric  acetate  gives  a  syrupy  acetate.  (HgCH). 
If  the  reaction  mixture  is  allowed  to  stand  for  several  months,  a  crystal- 
line form  of  the  acetic  separates.  (HgCH).  This  form  of  the  acetate 
consists  of  white  crystals  insoluble  in  water,  ether,  soluble  in  alcohol, 
especially  hot,  decomposed  by  hot  water.  Distilled  with  25%  phos- 
phoric acid  it  gives  safrol.  The  syrupy  acetate  resembles  glucose 
syrup,  it  is  soluble  in  alcohol,  practically  insoluble  in  ether,  soluble 
in  hot  water,  very  little  soluble  cold.  Hydrogen  sulfide  gives  HgS 
and  safrol.  The  crystalline  acetate  gives  a  crystalline  chloride  which 
decomposes  at  170°.  The  syrupy  acetate  gives  a  chloride  which  crystal- 
lizes from  hot  alcohol  in  hard  resetted  prisms  which  melt  at  138° 
(HgClCH).  Both  of  the  isomeric  chlorides  give  safrol  when  treated 
with  zinc  and  sodium  hydroxide.  The  chloride  which  melts  at  138° 
has  recently  been  obtained  by  Manchot122  from  the  reaction  mixture 
of  safrol  and  mercuric  acetate  in  water  treated  with  10%  sodium 
chloride.  He  describes  the  substance  as  crystallizing  from  alcohol  in 
long  white  star-clustered  monoclinic  needles  of  M.P.  136-7°.  The  sub- 
stance does  not  give  mercury  reactions  with  ammonium  sulfide,  sodium 
hydroxide  or  ammonium  hydroxide.  Warming  with  dilute  HC1  gives 
an  odor  of  safrol.  The  chloride  is  very  little  soluble  in  water,  very 
soluble  in  sodium  hydroxide,  reprecipitated  by  dilute  HOI.  (CHHgCl). 

The  corresponding  bromide,  C10H10O2Hg(OH)Br,  is  obtained  by 
treating  the  safrol  reaction  mixture  with  10%  potassium  bromide. 
The  crude  precipitate  melts  at  144°  and  gives  no  mercury  reactions 
with  ammonium  sulfide  or  ammonium  hydroxide.  It  is  recrystallized 
by  dissolving  in  alcohol  and  diluting  with  water.  It  forms  long  silky 
flat  white  needles.  M.P.  144-5°.  It  is  difficultly  soluble  in  water  and 
benzene,  very  soluble  in  sodium  hydroxide,  reprecipitated  by  hydro- 
chloric acid.  (CHBrHg) .  The  iodide  is  made  in  the  same  way  and  has 
entirely  similar  reactions  and  properties.  M.P.  152.5°  (CHHgl) .  One 
anomalous  property  is  its  reaction  with  sulfides.  It  does  not  react  with 
ammonium  sulfide  but  is  blackened  by  hydrogen  sulfide.123  This  differ- 
ence is  perhaps  due  to  some  protective  action  of  the  basic  solution. 

The  corresponding  hydroxide,  (C10H1002HgOH)OH,  as  Manchot 
formulates  it,  is  obtained  from  the  bromide  by  moist  silver  oxide. 

121  Balbiano   and   Paolini,    Ber.   35    (1902),    2998.      Balbiano   and   Paolini,    Her.    36 
(1903),  3578.     Balbiano,  Ber.  42   (1909),  1505.     Manchot,  Ann.  421   (1920),  320. 
322  Manchot,  loc.  cit.  320. 
188 /bid.  325. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      287 

The  aqueous  solution  obtained  is  slightly  alkaline  to  litmus  but  not  to 
phenolphthalein  or  curcumine.  HC1  gives  a  precipitate  of  the  chlo- 
ride. Heating  this  mixture  gives  an  odor  of  safrol.  The  base  treated 
with  potassium  bromide  gives  a  precipitate  of  the  bromide. 

Safrol  treated  with  three  molecules  of  mercuric  acetate  gives  a 
solution  from  which  a  chloride  precipitates  a  substance  which  Man- 
chot  thinks  may  be  C10H1002.HgCl2.HgO.  (CHHg)  . 

Eugenol   methyl   ether,    dimethyl    ether    of    p-allyl   pyrocatechol.12* 

(CHHg). 

The  acetate  obtained  is  a  mixture,  as  it  gives  two  isomeric  chlo- 
rides. One  of  these  chlorides  crystallizes  in  small  transparent  prisms, 
very  little  soluble  in  hot  water,  soluble  in  alcohol.  M.P.  112-113° 
(CHHgCl).  The  isomeric  chloride  is  formed  as  a  syrup  which  gradu- 
ally hardens.  It  is  amorphous.  (ClHg,  high).  Both  the  chlorides  give 
methyl  eugenol  on  treatment  with  zinc  and  sodium  hydroxide.  Man- 
chot  has  obtained  the  crystalline  chloride  by  treating  the  reaction  mix- 
ture containing  the  acetate  with  10%  sodium  chloride.125  He  obtained 
silky  needle  crystals  and  a  brown  smeary  product.  The  crystals  are 
soluble  in  water,  while  the  amorphous  product  is  insoluble.  The  crys- 
tals melt  at  112-5°  (CHHgCl).  Ammonium  hydroxide  and  ammonium 
sulfide  give  no  reaction.  Sodium  hydroxide  gives  a  white  precipitate, 
soluble  in  excess.  Hydrochloric  acid  gives  methyl  eugenol.  A  peculiar 
reaction  was  noted  by  Manchot  in  the  action  of  the  chloride  with  30 
per  cent  hydrogen  peroxide.  Mercuric  oxide  separates  at  once.  Con- 
siderable resin  is  formed  at  the  same  time. 

Isoapiol,  2,  5-  (or  2,  3-)  -Dimethyl  ether,  3,  4-  (or  4,  5-)-methylene  ether 
of  2,  3,  4,  5-tetrahydroxy-l-propenylbenzene.126 

This  propenyl  compound  not  only  reduces  mercuric  acetate  to  the 
mercurous  compound  forming  a  glycol  but  acts  further  with  mercuric 
acetate  giving  a  substance  which  may  be  a  ring  mercurated  compound. 
This  compound  softens  at  160°  and  melts  at  174°.  The  composition 
corresponds  to  "CH202  HgOAc.HgOAc" 


(CH30)2     C3H5(OH), 

124  Manchot,  loc.  cit.  326.     Balbiano,  loc.  cit. 

125  Manchot,  loc.  cit.  326. 

128  Balbiano  and  Paolini,  Ber.  36   (1903),  3583. 


COMPOUNDS  OF  MERCURY 

Apiol,  allyl  compound  corresponding  to  isoapiol.127  The  reaction  with 
mercuric  acetate  is  more  rapid  than  in  the  other  allyl  compounds 
studied.  Crystals  start  depositing  in  an  hour  and  the  reaction  is  ended 
in  about  five  hours.  The  acetate  is  recrystallized  from  alcohol.  Only 
one  acetate  is  obtained.  It  forms  fine  needles  almost  insoluble  in  wa- 
ter, little  soluble  in  cold  alcohol,  but  soluble  hot.  (CHHg).  M.P. 
157-8°.  Treatment  of  -the  acetate  with  zinc  and  sodium  hydroxide, 
followed  by  steam  distillation,  gives  apiol.128 

A  benzoyl  derivative  can  be  prepared.  This  is  an  oil  boiling  at 
165°at  4  mm.  Saponification  and  acidification  gives  hydroxyapiol 
and  benzoic  acid.  Eugenol  treated  with  three  molecules  of  mercuric 
acetate  gives  a  product  which  is  not  well  defined  but  may  be  C10H1:L02. 
HgCl2.Hg0.129 

Mercury  Derivatives  of  Saligenin.130 

Anhydride  of  2-Hydroxy-S,  5-dihydroxymercuribenzyl  Alcohol. 

Saligenin  is  refluxed  with  mercuric  acetate  in  alcohol  containing 
a  small  amount  of  acetic  acid.  On  standing  over  night  the  solution 
deposits  hard  aggregates  of  needle  crystals.  The  compound  is  insolu- 
ble in  water  and  common  solvents.  It  dissolves  in  hot  glacial  acetic 
acid,  in  hot  acetic  anhydride,  and  in  alkalies.  It  is  insoluble  in  am- 
monium hydroxide.  A  water  suspension  is  not  changed  by  hydrogen 
sulfide.  An  alkaline  solution  reacts  with  hydrogen  sulfide  giving  a 
black  precipitate  after  several  hours.  It  darkens  and  gradually  decom- 
poses on  heating  without  melting.  It  forms  insoluble  salts  with  chlo- 
rides, bromides,  iodides,  and  sulfides.  Its  nitrate  is  soluble.  The  so- 
dium compound  is  made  by  pouring  a  solution  in  sodium  hydroxide 
into  alcohol. 

The  dimercurated  saligenin  is  purified  by*  repeated  extractions  with 
hot  water,  alcohol,  and  ether.  It  is  then  dried  at  100°  (Hg).  The 
anhydride  is  believed  to  be  formed  by  the  elimination  of  water  be- 
tween the  phenolic  hydroxyl  and  the  —  HgOH  group  ortho  to  it.  When 
air  dried  it  contains  3.5  H20.  (Hg) . 

The  anhydride  reacts  with  hot  acetic  anhydride  giving  a  triacetate 
which  probably  has  acetate  groups  on  the  two  mercury  atoms  and  on 
the  alcohol  group.  (Hg) .  The  phenolic  hydroxyl  is  not  acetylated. 

127  Balbiano,  loc.  cit. 

128Balbiano,  Ber.  42   (1909),  1506. 

«» Manchot,  Ann.  421   (1920),  329. 

"°Hart  and  Hirschf  elder,  J.  Am.  Ohem.  Sdc.  42  (1920),  2680. 


DERIVATIVES  OF  PHENOLS,  NAPHTHOLS,  ETC.      289 

Mercury  Derivatives  of  p-Hydroxy-m-Nitrobenzyl  Alcohol.131 

8-Hydroxymercuri-4-hydroxy-5-nitrobenzyl  alcohol. 

The  substituted  carbinol  is  refluxed  with  alcoholic  mercuric  acetate 
and  a  little  acetic  acid.  After  cooling,  the  solution  deposits  yellow 
crystals.  The  product  is  only  slightly  soluble  in  water  and  is  insolu- 
ble in  common  solvents.  It  dissolves  completely  in  sodium  hydroxide 
except  for  a  trace  of  mercurous  compound.  The  alkaline  solution  has 
a  deep  reddish  yellow  color.  It  can  be  crystallized  from  hot  glacial 
acetic  acid  or  acetic  anhydride.  It  does  not  melt  at  240°.  An  aque- 
ous suspension  does  not  react  with  hydrogen  sulfide.  A  solution  in 
sodium  hydroxide  reacts  slowly  with  hydrogen  sulfide  giving  mercuric 
sulfide.  It  gives  the  following  insoluble  salts,  chloride,  bromide,  iodide, 
and  sulfate.  The  nitrate  is  soluble. 

The  mercury  compound  is  purified  for  analysis  by  crystallizing 
three  times  from  20  per  cent  acetic  acid.  Beautiful  long  light  yellow 
crystals  separate.  (Hg).  The  fact  that  the  substance  does  not  lose 
water  to  form  an  inner  anhydride  when  heated  at  110°  is  used  as 
evidence  that  the  —  HgOH  group  is  in  position  2,  that  is,  meta  to  the 
phenolic  hydroxyl.  Such  an  orientation  of  the  mercury  is  entirely  im- 
probable.132 Treatment  with  hot  acetic  anhydride  gives  a  mono- 
acetate  (Hg) .  The  acetate  group  is  probably  attached  to  the  mercury. 
If  that  is  the  case  the  acetate  is  8-Acetoxymercuri-4-hydroxy-5-nitro- 
benzyl  alcohol. 

181  Hart  and  Hirschfelder,  J.  Am.  Chem.  Soc.  42    (1920),  2683. 

132  >phe  position  of  the  mercury  has  been  proved  to  be  ortho  to  the  hydroxyl  group 
by  treating  the  mercury  compound  with  iodine  in  potassium  iodide  solution.  The 
product  is  3-iodo-4-hydroxy-5-nitrobenzyl  alcohol.  Oxidation  changes  this  to  the  corre- 
sponding benzoic  acid.  Kharasch,  J.  Am.  Chem.  Soc.  43  (1921),  1203. 


Chapter  XII. 
Mercury  Derivatives  of  Aromatic  Acids. 

Mercury  Derivatives  of  Benzoic  Acid.1 

Anhydride  of  o-hydroxymercuri  benzoic  acid. 

Pesci  originally  thought  that  the  product  of  the  mercuration  of  ben- 
zoic acid  had  the  mercury  in  the  para  position.  The  fact  that  it  is  in 
the  ortho  position  was  proved  by  Dimroth  and  confirmed  by  Pesci  by 
making  the  mercurated  benzoic  acid  from  phthalic  acid  and  mercuric 
e  with  the  elimination  of  C02.2 

-  C02H  +  Hg(OAc)2  ->   /\  —  C  =  0  +  C02  +  2HOAc. 
-C02H 

Preparation. 

1.  Anhydrous  mercuric  benzoate  is  heated  in  an  oil  bath  at  170° 
until  a  sample  dissolves  in  sodium  hydroxide.    The  resulting  product  is 
a  mixture  of  the  C  •—  Hg  compound  and  free  benzoic  acid.    The  latter 
is  washed  out  of  the  mixture  by  alcohol  and  ether.    The  residue  is  dis- 
solved in  the  least  possible  dilute  sodium  carbonate  solution.    The  pure 
anhydride  is  then  precipitated  by  passing  carbon   dioxide  into  the 
solution. 

2.  Benzoic  acid  is  fused  with  mercuric  acetate  until  the  reaction  is 
complete.    The  melt  is  cooled,  powdered  and  dissolved  in  ammonium 
hydroxide,  filtered,  and  boiled  with  sodium  carbonate  for  two  hours. 
The  solution  is  filtered,  cooled,  and  treated  with  carbon  dioxide  to 

1  Dimroth,  Ber.  32  (1899),  765.     Chem.  Zentr.  1899  I  936.  Pesci,  Atti.  accad.  Lincei 
(5)   9  I   (1900),  255.     Chem.  Zentr.  1900  I  1097.     Dimroth,   Chem.  Zentr.  1901  I  449. 
Pesci,  Atti  acoad.  Lincei  (5)   10  I   (1900),  362.     Chem.  Zentr.  1901  II  108.     Sand  and 
Singer,  Ber.  35   (1902),  3170.     Dimroth,  Ber.  35   (1902),  2872.     Pesci,  Gazz.  chim.  ital. 
32  II  (1902),  280.     Chem.  Zentr.  1902  I  1454.     D.  R.  P.  229,574.     Chem.  Zentr.  1911  I 
275.     D.  R.  P.  229,781.     Chem.  Zentr.  1911  I  276.      Sachs,  Ber.  53    (1920),  1740. 

2  Pesci,  Atti  accad.  Lincei  (5)   10  I   (1901),  362. 

290 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      291 

precipitate  the  anhydride.  This  is  dissolved  in  ammonium  carbonate 
solution  which  is  then  precipitated  by  an  excess  of  acetic  acid. 

3.  When  a  solution  of  sodium  phthalate  is  boiled  with  mercuric 
acetate  and  a  little  acetic  acid  carbon  dioxide  is  evolved  and  the 
anhydride  is  precipitated. 

Properties. 

White  poorly  crystalline  powder,  almost  insoluble  in  all  common 
solvents,  soluble  in  solutions  of  alkalies  and  alkaline  carbonates.  It 

,—  C02H 

is  fairly  stable  to  mineral  acids  forming  salts  of  the  type  '  —  HgX    . 

,—  CO2Na 
Sodium  hydroxide  gives  a  salt,  '  —  HgOH  .    Salts  like  sodium  chloride 

r—  C02Na 
form  the  third  type  of  salt,  '  —  HgCl     .      All  these  salts  have  a  strong 

tendency  to  hydrolyze  and  are  therefore  hard  to  prepare  in  the  pure 
state.  Boiling  with  an  excess  of  an  inorganic  halide  tends  to  split  the 
C  —  Hg  linkage  forming  a  benzoate  and  a  molecule  of  free  base. 

-  C  =  0  +  2NaX  +  H20  -»  C6H5  —  C02Na  +  HgX2  +  NaOH. 


The  splitting  effects  of  the  halides  decrease  from  the  iodide  to  the  chlo- 
ride. Excess  of  mineral  acids  gives  benzoic  acid  and  mercuric  salts. 
Bromine  forms  ortho  bromobenzoic  acid.  Thionyl  chloride  gives  a  60 
per  cent  yield  of  o-chloromercuribenzoyl  chloride. 


Salts  of  the  type, 


Salts  of  this  type  may  be  made  by  treating  the  anhydride  with  a 
slight  excess  of  the  proper  dilute  acid.  They  can  also  be  made  by 
adding  the  salt  NaX  and  acidifying  with  dilute  acetic  acid.  These 
salts,  as  a  rule,  are  only  sparingly  soluble  in  water  and  alcohol.  Salts 
have  been  prepared  in  which  X  =  Cl,  Br,  I,  S,  and  —  SC2H5.  The 
salts  have  no  melting  points.  In  general  their  reactions  have  not  been 
studied.  Thionyl  chloride  gives  very  little  action  with  o-chloromercuri- 
benzoic  acid.  This  same  substance  reacts  with  ethyl  mercaptan  at 


292  COMPOUNDS  OF  MERCURY 

150°  to  form  benzole  acid  and  ethyl  mercaptide  mercuric  chloride, 
C2H5  — S  — HgCl.3 

o-Ethylmercaptomercuribenzoic  acid  reacts  with  thionyl  chloride 
to  give  the  —  HgCl  compound.4  The  sulfide  (RHg)2S  when  heated 
gives  mercuric  sulfide  and  mercuribis-o-benzoic  acid.5 


Salts  of  the  type, 


This  type  of  salt  is  made  by  dissolving  the  anhydride  in  a  solution 
of  the  base  or  by  treating  such  a  solution  with  a  salt  of  the  desired 
metal.  These  salts,  as  a  general  rule,  are  more  soluble  than  the  pre- 
ceding type.  Salts  have  been  made  in  which  M  —  NH4,  Ba,  Ca,  Mg, 
Ag,  isoamylammonium  and  benzylammonium.  Other  salts  have  been 
made  in  solution  but  cannot  be  isolated.6 

,/\— C02M 
Salts  of  the  type, 

V/-HgX 

These  salts  are  made  by  treating  the  anhydride  with  a  solution  of 
MX.  They  are  rather  more  stable  than  the  salts  of  the  second  type. 
When  X  =  Cl  salts  have  been  made  with  M  —  Na,  K,  NH4,  Ba,  and 
phenylammonium.  With  X  =  Br,  M  =  Na,  K,  and  Ba.  With  X  =  I, 
M  =  Na,  K,  and  Ba.  When  X  =  S,  M  =  Na  and  K.  Other  salts 
have  been  obtained  in  solution.  Tfre  sodium  salt  of  o-chloromercuri- 
benzoic  acid  reacts  with  ethyl  mercaptan  in  the  cold  forming  o-mer- 
captomercuribenzoic  acid.  This  is  in  sharp  contrast  to  the  action  of 
the  free  acid  which  gives  no  reaction  up  to  150°  and  then  only  with 
the  splitting  of  the  C  —  Hg  linkage. 

Mercury  Derivatives  of  Benzoic  Ester.7 

o-Chloromercuribenzoic  methyl  ester.8 

Benzoic  ester  does  not  react  with  mercuric  acetate  in  the  cold  even 
on  standing  for  months.  When  powdered  mercuric  acetate  is  refluxed 

»  Sachs,  loc.  cit.  1743. 

*Z6i#.  1745. 

"Pesci,  #oz£.  cMm.  ital.  32  II  (1902),  292.     Chem.  Zentr.  1902  II  1454. 

•  D.  R.  P.  261,875.     Chem.  Zentr.  1913  II  395. 

TSchoeller  and  Hueter,  B&r.  47  (1914),  1932.  Schoeller  and  Schrauth,  Ber.  53 
(1920),  636.  Sachs,  Ber.  53  (1920),  1739. 

•  Schoeller  and  Schrauth,  loc.  cit. 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      293 

with  methyl  benzoate  and  a  small  amount  of  acetic  acid  for  four  hours 
a  side  test  shows  no  more  mercuric  ions.  A  small  amount  of  mercurous 
acetate  and  mercury  has  to  be  filtered  off.  Evaporation  of  the  fil- 
trate in  a  vacuum  leaves  a  yellow  oil.  When  acetone  is  added  about 
one-quarter  of  the  oil  is  precipitated  as  an  amorphous  solid.  The 
mercury  content  corresponds  to  a  di-acetoxymercuribenzoic  ester. 
Evaporation  of  the  acetone  solution  leaves  a  slightly  yellow  resin. 
When  this  is  dissolved  in  water  and  treated  with  sodium  chloride  solu- 
tion a  precipitate  of  chloromercuribenzoic  methyl  ester  is  obtained. 
This  is  purified  by  dissolving  it  in  ethyl  acetate  and  precipitating  it 
with  low  boiling  ligroin.  (CHHgCl).  It  is  fairly  soluble  in  alcohol, 
ethyl  acetate,  chloroform,  less  in  ether,  practically  insoluble  in  low 
boiling  ligroin  and  water.  It  sinters  142°,  melts  162°.  Ammonium 
sulfide  gives  HgS  only  on  long  warming.  This  chloride  has  also  been 
made  by  boiling  sulfidemercuribenzoyl  chloride  with  methyl  alcohol. 
Prepared  in  this  way  it  has  a  melting  point  of  182°. 9  Since  the  ben- 
zoyl  chloride  was  made  from  the  mercury  benzoic  anhydride  which  is 
known  to  have  the  mercury  in  the  ortho  position  the  proof  of  the 
identity  of  these  two  chloromercuribenzoic  esters  would  confirm  the 
assumption  that  the  mercuration  of  benzoic  ester  goes  in  the  same  way 
as  that  of  benzoic  acid. 

Sulfidemercuribenzoic  methyl  ester.     S(— Hg  — CaH4  — C02CH3)2.10 

The  chloride  is  dissolved  in  warm  methyl  alcohol  and  cooled  and 
treated  with  one-half  mole  of  a  methyl  alcohol  solution  of  hydrogen 
sulfide.  An  amorphous  white  precipitate  is  formed.  An  excess  of 
hydrogen  sulfide  must  be  avoided  as  it  dissolves  the  precipitate.  The 
precipitate  is  filtered  at  once  as  it  turns  yellow  on  standing  in  the 
mother  liquor.  It  forms  a  white  amorphous  powder,  which  blackens 
on  heating.  (SHg).  It  is  slightly  soluble  in  alcohol,  ethyl  acetate, 
acetone,  ether,  and  low  boiling  ligroin,  easily  soluble  in  chloroform, 
benzene,  and  aniline.  All  of  these  solutions  slowly  darken.  It  is 
soluble  in  excess  of  hydrogen  sulfide  or  sodium  sulfide  solutions  ap- 
parently forming  soluble  compounds  containing  the  gKmpings  —  HgSH 
and  —  HgSNa. 

•Sachs,  loc.  cit.  1741. 

10  Schoeller  and  Schrauth,  loc.  cit.  637. 


294  COMPOUNDS  OF  MERCURY 

o-M ercuribis- (benzole  methyl  ester). ^ 

The  sulfide  is  heated  3  hours  at  120°.  The  residue  is  cooled  and 
extracted  with  ethyl  acetate  leaving  HgS  behind.  Spontaneous  evapo- 
ration of  the  extracts  gives  white  crystals  in  90  per  cent  yield.  These 
are  recrystallized  from  alcohol  and  ether.  (CHHg) .  It  does  not  react 
with  sodium  stannite.  It  is  soluble  in  methyl  and  ethyl  alcohol,  ace- 
tone, ethyl  acetate,  chloroform,  benzene,  difficultly  soluble  in  water  and 
ligroin.  Saponification  gives  mercuribis- (benzoic  acid). 

o-Chloromercuribenzoyl  chloride.12 

The  pure  anhydride  is  treated  with  an  excess  of  thionyl  chloride. 
The  reaction  starts  instantly.  The  precipitate  is  washed  with  chloro- 
form. It  consists  of  needle  crystals  and  an  amorphous  substance.  Ex- 
traction with  benzene  leaves  most  of  the  latter  substance  undissolved. 
M.P.  173.5°  (not  complete)  (ClHg).  When  dissolved  in  ether  and 
treated  with  dry  hydrogen  sulfide  it  gives  o-sulfidemercuribenzoyl 
chloride,  S(HgC6H4 —  COC1)2,  a  slightly  yellow  precipitate  which 
does  not  melt  at  230°.  It  reacts  with  concentrated  hydrochloric 
acid  giving  hydrogen  sulfide.  It  does  not  react  with  mercuric  oxide, 
showing  that  it  does  not  contain  the  grouping  —  CO.S — .  (CHSHg). 
When  boiled  with  methyl  alcohol  it  gives  HC1,  HgS,  methyl  benzoate, 
and  o-chloromercuribenzoic  methyl  ester.  When  chloromercuribenzoyl 
chloride  is  refluxed  with  methyl  mercaptan  in  benzene  solution  it  gives 

HgCl 

/ 

chloromercurithiobenzoic  ethyl  ester.     C6H4  This  sub- 

\ 
CO.SC2H5. 

stance  forms  slightly  yellow  rhombic  leaflets,  soluble  in  alcohol,  ether, 
benzene,  chloroform,  and  acetone.     (CH). 

o-Mercuribis-benzoic  acid.13 
Preparation.     # 

1.  A  solution  of  the  sodium  salt  of  o-hydroxymercuribenzoic  acid 
is  precipitated  frr  the  calculated  amount  of  sodium  sulfide.  Long 

11  Ibid. 

12  Sachs,  loc.  cit. 

"Pesci,  Atti  accad.  lAncei  (5)  10  I  (1901),  413.  Ghent.  Zentr.  1901  II  108. 
J.  Cher*.  Soc.  80  (1901),  624.  Gazz.  chim.  ital.  32  II  (1902),  293.  Schoeller  and 
Schrauth,  loc.  cit.  638. 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      295 

boiling  of  the  mixture  gives  mercuric  sulfide  and  a  solution  of  the 
sodium  salt  of  o-mercuribis-benzoic  acid.  This  can  be  precipitated 
as  the  calcium  salt,  then  changed  to  the  pure  sodium  salt  by  sodium 
carbonate  and  finally  acidified  with  acetic  acid  to  precipitate  the 
pure  acid.  This  forms  needles  from  hot  alcohol,  insoluble  in  water.  It 
decomposes  on  heating  without  melting.  Several  salts  have  been  made 
and  analyzed. 

2.  By  the  saponification  of  o-mercuribis-benzoic  ester  by  alco- 
holic sodium  hydroxide.14  (CHHg).  It  is  soluble  in  alcohol,  chloro- 
form, and  hot  water. 

Miscellaneous  references  on  mercury  benzoic  acid  compounds.15 

Mercury  Derivatives  of  Substituted  Benzoic  Acids. 

Anhydride  of  o-hydroxymercuri-o'-chlorobenzoic  acid.™ 

The  anhydride  is  made  by  heating  the  mercury  salt  of  the  acid 
to  140°  until  the  substance  is  alkali  soluble.    It  is  insoluble  in  water, 
alcohol,  and  ether.    With  glutarimide  it  forms  a  crystalline  compound 
which  is  water  soluble.    With  sodium  hydroxide  it  gives  a  soluble  salt. 
The  sodium  salt  of  m-chlorobenzoic  acid  heated  with  mercuric  ace- 
tate in  water  gives  a  white  powder  which  is  soluble  in  sodium  chloride 
solution.16a    It  gives  a  yellow  precipitate  with  sodium  hydroxide. 
The  anhydride  of  2-hydroxymercuri-S,  5-dibromobenzoic  acid.17 
The  anhydride  of  o-hydroxymercuri-o-iodobenzoic  acid.18 
The  anhydride  of  o-hydroxymercuri-o'-nitrobenzoic  acid 19  is  obtained 
by   heating   the  mercury   salt   of   o-nitrobenzoic   acid   at   200°.     If 
this  compound  is  reduced  in  alkaline  or  neutral  medium  by  one  equiva- 
lent of  hydrogen  for  each  mole  of  the  anhydride  it  gives  o-mercuri- 
bis-o' '-nitrobenzoic  acid.    If  the  reduction  is  carried  further  the  cor- 
responding amino  compound  is  obtained. 

"  Schoeller  and  Schrauth,  ibid. 

15Schoeller  and  Schrauth,  Biochem.  Z.  32  (1911),  511.  Schoeller  and  Schrauth 
and  Miiller,  Biochem.  Z.  33  (1911),  403.  Schoeller  and  Schrauth,  D.  R.  P.  248,291. 
Ghem.  Zentr.  1912  II  211.  Chem.  Abet.  8  (1914),  21,  231.  D.  R.  P.  249,332.  Chem. 
Zentr.  1912  II  465.  D.  R.  P.  234,914.  Frankel,  Die  Arzneimittelsynthese,  1919,  p,  665. 
Devillers,  Chem.  Abst.  7  (1913),  1580. 

16  D.  R.  P.  229,574.  Chem.  Zentr.  1911  I  275.  Schrauth,  Seifensieder  Ztg.  37 
(1910),  1276,  1323.  Chem.  Zentr.  1911  I  695.  D.  R.  P.  234,914.  Chem.  Zentr.  1911 
II  112.  D.  R.  P.  234,054.  Frankel,  p.  665. 

iea  private  communication,   G.  W.   Raiziss. 
•     "  D.  R.  P.  249,332.     Frankel,  p.  665.     Chem.  Zentr.  1912  II  465. 

18  D.  R.  P.  234,914.     Frankel,  p.  665.     Chem.  Zentr.  1911  II  112. 

18  D.  R.  P.  251,332.     Frankel,  p.  670.     D.  R.  P.  249,725,  ibid. 


296  COMPOUNDS  OF  MERCURY 

m-Nitrobenzoic  acid  when  heated  with  mercuric  acetate  gives 
products  containing  one  and  two  atoms  of  mercury.  The  position  of 
the  mercury  groups  has  not  yet  been  determined.20  Heating  the  mer- 
curic salt  of  m-nitrobenzoic  acid  gives  two  products  each  containing 
one  atom  of  mercury.21  One  still  contains  a  carboxyl  group  and  is 
soluble  in  alkali.  The  other  has  lost  a  molecule  of  carbon  dioxide 
and  is  insoluble  in  alkali. 

The  anhydride  of  o-hydroxymercuri-p-nitrobenzoic  acid22  is  ob- 
tained by  heating  the  mercury  salt  of  p-nitrobenzoic  acid  at  200°.  It 
can  be  reduced  by  stannous  chloride  or  ferrous  hydroxide  to  o-mercuri- 
bis-p-nitrobenzoic  acid.  This  is  a  yellow  powder  which  is  decomposed 
by  heat  giving  an  odor  of  nitrobenzene.  It  is  soluble  in  alkalies.  The 
concentrated  solution  in  sodium  hydroxide  when  treated  with  alcohol 
gives  a  disodium  salt  as  a  yellow  flocculent  precipitate.  The  sodium 
salt  is  soluble  in  water.  Its  solution  gives  precipitates  with  solutions 
of  heavy  metal  salts.  Further  reduction  in  neutral  or  alkaline  solu- 
tion gives  o-mercuribis-p-aminobenzoic  acid. 

Derivatives  of  sym-dinitrobenzoic  acid.23 

The  anhydride  is  made  in  the  usual  way.  When  reduced  by 
stannous  chloride  or  ferrous  hydroxide  it  yields  2,  2'-mercuribis-3,  5  di- 
nitrobenzoic  acid,  a  yellow  powder  insoluble  except  in  solutions  of 
bases.  Its  disodium  salt  is  a  crystalline  yellow  powder. 

Derivatives  of  Anthranilic  Acid.24 

N-iso  di-acetoxymercuri  anthranilic  methyl  ester, 

AcOHg  —  C6H3  (C02Me)  —  NH  —  HgOAc.H20. 

Equal  molecules  of  methyl  anthranilate  and  mercuric  acetate  are 
mixed  in  80  per  cent  methyl  alcohol.  In  a  few  minutes  a  white  floccu- 
lent precipitate  fills  the  solution.  After  1.5  hours  a  sample  gives  no 
mercuric  oxide  with  sodium  hydroxide.  The  water  of  crystallization 

20  Unpublished  results,  Whitmore  and  V.  E.  Meharg. 

21  Private  communication,  M.  S.  Kharasch. 

22  Blumenthal   and    Oppenheim,    Biochem.   Z.   32    (1911),    60;    35    (1911)    505;    39 
(1912),   54,  58;   57    (1913),   277;   65    (1914),   461.      D.   R.   P.   251,332.      Chem.   Z&ntr. 
1912  II  1413.     D.  R.  P.  249,725.     Chem.  Abst.  6  (1912),  1467. 

28  D.  R.  P.  251,332  loc.  cit. 

2*Schoeller  and   Hueter,   Bar.    47    (1914),    1930.     Schoeller,   Schrauth.   and   Liese, 
B&f.  52  (1919),  1777.     Schoeller  and  Schrauth,  Ber.  53   (1920),  634. 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      297 

cannot  be  removed  even  at  75°  in  a  vacuum  without  decomposition. 
(CHHg).  On  standing  in  the  mother  liquor  containing  the  unused 
methyl  anthranilate  the  amorphous  precipitate  changes  completely  to 
slightly  yellow  needle  crystals  of  the  acetoxymercuri  anthranilic  ester. 
The  "N-isodiacetate"  is  soluble  in  acetic  acid.  If  this  solution  is  neu- 
tralized with  ammonium  hydroxide  and  treated  with  ammonium  sul- 
fide,  one-half  of  the  mercury  is  precipitated  as  mercuric  sulfide.  Cold 
dilute  hydrochloric  acid  changes  the  "N-iso  diacetate"  to  mercuric 
chloride  and  chloromercuri  anthranilic  ester.  In  each  of  these  reactions 
the  N  —  Hg  linkage  is  broken  while  the  C  —  Hg  is  left  intact.  It  is 
also  soluble  in  hot  water,  hot  methyl  and  ethyl  alcohols,  almost  in- 
soluble in  acetone,  chloroform,  benzene,  and  low  boiling  ligroin.  The 
hot  aqueous  or  alcoholic  solution  on  cooling  forms  a  jelly.  The  "N-iso 
diacetate"  dissolved  in  methyl  alcohol  and  heated  for  half  an  hour 
with  an  acetic  acid  solution  of.  methyl  anthranilate  gives  crystals 
of  acetoxymercuri  anthranilic  ester,  in  almost  quantitative  yield.  If 
the  "N-iso  diacetate"  is  heated  alone  with  acetic  acid  and  methyl 
alcohol  for  half  an  hour  at  50°  it  gives  diacetoxymercuri  anthranilic 

NH2 

methyl  ester.    AcOHg  — /N— C02Me. 

HgOAc 

Acetoxymercuri  anthranilic  methyl  ester. 

The  "N-iso  diacetate"  is  suspended  in  methyl  alcohol  and  heated 
with  the  calculated  amount  of  methyl  anthranilate  dissolved  in  a  little 
acetic  acid.  Solution  is  complete  after  heating  half  an  hour  at  50°. 
Crystals  soon  begin  to  separate.  After  standing  in  ice  for  24  hours 
the  mixture  is  filtered.  M.P.  178-80°  (corr.  180-182°).  A  better 
method  of  making  the  compound  is  to  treat  methyl  anthranilate  with 
one  mole  of  mercuric  acetate  in  methyl  alcohol  and  acetic  acid  at  50°. 
The  reaction  is  complete  in  about  15  minutes  as  is  shown  by  a  side 
test  with  ammonium  sulfide.  On  cooling,  yellow  needles  separate. 
Yield  90%  (CHNHg) .  It  is  easily  soluble  in  boiling  water,  hot  methyl 
or  ethyl  alcohol,  ammonium  hydroxide,  acetic  acid,  more  difficultly 
in  benzene,  ethyl  acetate,  and  acetone,  very  little  in  chloroform.  It 
gives  no  action  with  ammonium  sulfide. 


298  COMPOUNDS  OF  MERCURY 

Chloromercuri  anthranilic  methyl  ester. 

The  acetate  in  alcohol  solution  is  mixed  with  a  dilute  solution  of 
sodium  chloride.  It  forms  small  needles,  soluble  in  the  usual  organic 
solvents  especially  in  ethyl  acetate  from  which  it  may  be  precipitated 
by  petrol  ether.  M.P.  182°  (corr.  184°)  (ClHg).  The  corresponding 
bromide  is  made  in  the  same  way.  It  forms  fine  white  needles  when 
recrystallized  from  water.  M.P.  178°  (BrHg).  The  iodide  is  made  in 
the  same  way.  Recrystallized  from  alcohol  it  forms  small  needles. 
M.P.  171-2°  (corr.  173-4°).  (IHg). 

Anhydride  of  2-amino-5-hydroxymercuri-benzoic  acid. 

The  acetate  of  the  mercurated  ester  is  suspended  in  water  and 
treated  with  2.25  moles  of  normal  sodium  hydroxide.  Solution  takes 
place  on  boiling.  After  cooling  the  solution  is  treated  with  1.25 
equivalents  of  normal  sulfuric  acid  which  forms  a  white  flocculent 
precipitate.  An  excess  of  acid  dissolves  the  precipitate.  M.P.  212- 
214°  (decomp.)  (CHNHg).  It  is  easily  soluble  in  water  solutions  of 
potassium  iodide,  potassium  cyanide,  and  sodium  thiosulfate,  less 
soluble  in  potassium  bromide  and  still  less  in  potassium  chloride.  It 
is  very  little  soluble  in  organic  solvents.  It  dissolves  easily  in  am- 
monium hydroxide,  ammonium  carbonate,  dilute  sodium  hydroxide  and 
sodium  carbonate  solution.  An  ammonium  hydroxide  solution  treated 
with  ammonium  sulfide  gives  no  HgS  until  heated  or  after  long  stand- 
ing. Another  method  of  making  the  anhydride  is  by  heating  pure 
anthranilic  acid  with  freshly  prepared  mercuric  oxide  and  water.  The 
heating  is  best  done  by  a  vigorous  jet  of  steam  passed  into  the  sus- 
pension. The  reaction  is  complete  when  a  sample  dissolves  in  alkali. 
The  solid  is  dissolved  in  1.25  moles  of  sodium  hydroxide,  filtered,  and 
precipitated  by  an  equivalent  amount  of  sulfuric  acid.  Yield  96%. 
Decomp.  210°  (CHNHg). 

The  anhydride  reacts  with  iodine  dissolved  in  potassium  iodide 
solution  giving  an  iodoanthranilic  acid  melting  at  210.5°,  with  decom- 
position, showing  that  the  mercury  occupied  the  position  para  to  the 
amino  group.  A  solution  of  the  anhydride  in  sodium  hydroxide  can 
be  used  to-  make  various  heavy  metal  salts  by  precipitation.  The 
copper  salt  is  a  light  green  amorphous  substance.  (Cu). 

1 'odomercuri- anthranilic  acid. 

The  anhydride  is  dissolved  in  potassium  iodide  solution.  The  dark 
brown  solution  is  filtered  from  a  small  amount  of  yellow  green  residue. 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      299 

The  filtrate  is  diluted  and  treated  with  the  calculated  amount  of  .1  N 
sulfuric  acid.  An  excess  of  acid  splits  mercuric  iodide  from  the  com- 
pound. (CHNHgl).  It  is  very  difficultly  soluble  in  water  and  organic 
solvents,  easily  soluble  in  alkalies,  decomposed  by  dilute  acids. 

Diacetoxymercuri-anthranilic  methyl  ester. 

Prepared  from  anthranilic  methyl  ester  and  2  moles  of  mercuric 
acetate  in  methyl  alcohol  and  acetic  acid  heated  one  hour  at  50°.  The 
crystals  obtained  contain  a  trace  of  mercurous  acetate.  It  is  recrystal- 
lized  from  methyl  alcohol  and  a  small  amount  of  acetic  acid.  (CHHg). 
M.P.  218-220°  (corr.  221-222°),  decomp.  It  is  soluble  in  organic  sol- 
vents but  less  so  than  the  monomercury  compound.  The  compound 
can  also  be  made  by  heating  the  "N-iso  diacetate"  with  acetic  acid 
and  methyl  alcohol  at  50°. 

Anhydride-  of  dihydroxymercuri-anthranilic  acid. 

The  diacetate  is  suspended  in  water  and  treated  with  3.25  moles  of 
normal  sodium  hydroxide.  The  boiled  solution  is  cooled  and  treated 
with  1.25  equivalents  of  normal  sulfuric  acid.  A  slightly  yellow  green 
amorphous  precipitate  separates.  Poor  analysis  for  CHHg.  The  sub- 
stance could  not  be  purified. 

5,  5f-Mercuribis-2-aminobenzoic  methyl  ester, 

Hg[C6H3(C02Me)—  NH2]2.25 

The  acetate  is  dissolved  in  the  least  amount  possible  of  75  per  cent 
alcohol  and  treated  with  a  concentrated  solution  of  sodium  thiosulfate. 
An  amorphous  white  precipitate  forms  at  once.  After  standing  1.5 
hours  at  45°  the  mixture  is  evaporated  in  a  vacuum  and  the  residue 
is  extracted  with  ethyl  acetate,  filtered,  evaporated,  and  treated  with 
low  boiling  ligroin  to  form  a  slight  turbidity.  On  cooling  light  yellow 
needles  form.  Yield  65  per  cent.  (CHNHg) .  It  is  easily  soluble  in 
methyl  and  ethyl  alcohols,  ethyl  acetate,  acetone,  chloroform,  benzene, 
difficultly  soluble  in  ligroin  and  water.  M.P.  196-7°  corr.,  after  slight 
darkening. 

6,  6f-Mercuribis-2-aminobenzoic  acid.26 

It  is  prepared  by  neutral  or  alkaline  reduction  of  the  anhydride  or 
salts  of  6-hydroxymercuri-2-nitrobenzoic  acid.27 

25  Schoeller  and  Schrauth,  ibid.  642. 

28  D.  R.  P.  249,725.     Frankel,  670. 

27  Blumenthal  and  Oppenheirn,  Biochem.  Z.  57  (1913),  288;  65  (1914),  460. 


300  COMPOUNDS  OF  MERCURY 

Derivatives  of  acetyl  anthranilic  acid.28 
Acetoxymercuri  acetyl  anthranilic  methyl  ester, 

AcOHg  —  C6H3  (C02Me)  —  NH  —  COCH3. 

In  sharp  contrast  to  anthranilic  ester  the  acetylated  compound  must 
be  refluxed  for  some  time  with  mercuric  acetate  solution  to  complete 
the  reaction.  Even  then  only  a  monomercurated  compound  is  ob- 
tained. When  the  two  substances  stand  in  cold  alcoholic  solution  for 
1.5  days  only  one-tenth  of  the  mixture  has  reacted.  Refluxing  for  two 
hours  in  water  solution  or  for  seven  hours  in  methyl  alcohol  completes 
the  reaction.  Another  and  more  rapid  preparation  is  from  the  two 
substances  heated  without  any  solvent  at  120-130°  for  half  an  hour. 
Any  unchanged  ester  is  extracted  with  ether  and  the  mercury  com- 
pound is  recrystallized  from  dilute  alcohol  in  which  it  is  very  soluble. 
The  mercury  compound  remaining  in  the  mother  liquors  can  be  pre- 
cipitated as  the  chloride  by  means  of  sodium  chloride.  (CHNHg) .  It 
forms  large  plates  from  dilute  alcohol,  which  are  very  soluble  in  or- 
ganic solvents  except  ether  and  ligroin.  M.P.  210°  (corr.  212°). 

Chloromercuri  acetyl  anthranilic  methyl  ester. 

The  mother  liquors  from  the  crystallization  of  the  acetate  from 
dilute  alcohol  are  precipitated  by  dilute  sodium  chloride.  It  is  recrys- 
tallized from  ethyl  acetate.  (CHHg).  It  is  little  soluble  in  common 
solvents,  best  in  hot  ethyl  acetate  from  which  it  forms  fine  needles. 
On  rapid  heating  it  melts  at  245-6°. 

Sodium  salt  of  %-hydroxymercuri-5-acetaminobenzoic  acid.29 

It  is  prepared  from  the  corresponding  anhydride  by  sodium  hy- 
droxide. 

Derivatives  of  Alkylanthranilic  Acids. 

Acetoxymercuri  methylanthranilic  methyl  ester,30 

AcOHg  — C6H3(C02Me)  —  NHCH3. 

Methylanthranilic  methyl  ester  reacts  about  as  rapidly  with  mer- 
curic acetate  as  does  the  unmethylated  ester  but  no  intermediate 
N  —  Hg  compound  and  no  di-acetoxymercuri  compound  can  be  ob- 

28  Schoeller  and  Hueter,  Ber.  47  (1914),  1946.     Frankel,  Die  Arzneimittelsynthese, 
1919,  p.  669.     D.  R.  P.  234,054.     Frankel,  665. 

29  Frankel,  665  and  669.     Blumenthal  and  Oppenheim,  Biochem.  Z.  57   (1913),  260. 
80  Schoeller  and  Hueter,  loc.  cit.  1940.     Schoeller  and  Schrauth,  D.  R.  P.  248,291. 

Chem.  Zentr.  1912  II  211.     Frankel,  662. 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      301 

tained.  In  methyl  alcohol  solution  all  mercuric  ions  disappear  after 
one-half  hour  in  the  cold.  Yield  97  per  cent.  It  is  recrystallized 
from  methyl  alcohol.  (CHNHg).  M.P.  198°  (corr.  200°),  decomp.  It 
is  very  easily  soluble  in  chloroform  and  hot  acetic  acid,  easily  soluble 
in  boiling  methyl  and  ethyl  alcohols,  ethyl  acetate,  acetone  and  ben- 
zene, only  slightly  soluble  in  boiling  water.  It  forms  needles  from 
alcohol. 

Chloromercuri  methylanthranilic  methyl  ester. 

It  is  prepared  from  the  acetate  and  crystallizes  from  alcohol  in 
white  needles.  M.P.  210-212°,  turning  violet.  (ClHg).  The  corre- 
sponding bromide  is  made  in  the  same  way  and  crystallizes  from 
ethyl  acetate  in  which  it  is  fairly  soluble  even  in  the  cold.  M.P.  215°, 
turning  violet.  (BrHg) .  The  iodide  is  similar  to  the  bromide.  M.P. 
190-191°,  after  turning  brown.  (IHg). 

Anhydride  of  hydroxymercuri  methylanthranilic  acid. 

It  is  prepared  from  a  suspension  of  the  acetate  treated  with  sodium 
hydroxide  and  sulfuric  acid  in  the  usual  way,  as  a  greenish  yellow 
amorphous  precipitate.  It  decomposes  without  melting  at  203° 
(CHNHg).  The  anhydride  can  also  be  prepared  by  boiling  a  solution 
of  methylanthranilic  acid  with  mercuric  oxide.  This  reaction  is  rapid, 
going  to  completion  in  about  fifteen  minutes.  Anthranilic  acid  itself 
requires  three  hours  for  the  completion  of  this  reaction.  The  an- 
hydride is  soluble  in  potassium  iodide  solution. 

lodomercuri  methylanthranilic  acid. 

It  is  prepared  from  the  anhydride  by  dissolving  in  potassium  iodide 
solution,  filtering  off  the  slight  solid  residue,  diluting  and  neutralizing 
with  sulfuric  acid.  It  is  soluble  in  alkalies  but  is  more- stable  to  acids 
than  the  corresponding  compound  containing  a  free  NH2  group.  It 
is  practically  insoluble  in  all  organic  solvents.  (CHNHgl). 

Acetoxymercuri  ethylanthranilic  ethyl  ester, 3i 

AcOHg  —  C6H3  (C02Et)  —  NH  —  C2H5. 

The  reaction  between  the  ester  and  mercuric  acetate  in  methyl 
alcohol  is  complete  in  an  hour  and  a  half.  It  crystallizes  from  methyl 
alcohol  in  needles.  (CHNHg).  M.P.  176°  (corr.  178°),  decomp.  It  is 
easily  soluble  in  hot  organic  solvents,  only  slightly  soluble  in  boiling 

11  Schoeljer  an<J  Hueter,  loc,  cit.  1943. 


302  COMPOUNDS  OF  MERCURY 

water.  The  corresponding  mercurated  methyl  ester  of  ethylanthranilic 
acid  is  made  in  the  same  way  and  has  similar  properties.  On  rapid 
heating  it  melts  at  187°  (corr.  189°)  (Hg). 

Acetoxymercuri  dimethylanthranilic  methyl  ester,52 

AcOHg  —  C6H3  (C02Me)  —  N  (CH3)  2. 

Prepared  in  the  usual  way  in  methyl  alcohol.  The  reaction  is  com- 
plete in  three  hours.  77%  yield.  Prismatic  crystals.  It  is  crystallized 
from  methyl  alcohol.  M.P.  133°  (corr.  134°).  It  is  easily  soluble  in 
organic  solvents. 

C hloromercuri  dimethylanthranilic  methyl  ester. 

It  is  prepared  from  the  acetate  and  recrystallized  from  methyl  alco- 
hol. It  forms  white  needles  which  gradually  change  to  prisms.  The 
first  crystals  contain  1  H20.  (ClHg).  M.P.  162-3°.  The  bromide  is 
made  like  the  chloride.  White  needles  M.P.  164°.  The  crystals  con- 
tain 1  H20.  (H20,Hg) .  The  water  is  lost  at  100°  in  vacuum.  (BrHg) . 
The  iodide  forms  white  needles  from  methyl  alcohol.  These  gradually 
change  to  prisms.  M.P.  159°  (IHg). 

Sulfatemercuri  dimethylanthranilic  acid. 

This  sulfate  is  obtained  when  an  attempt  is  made  to  make  the  an- 
hydride from  the  acetate  by  the  usual  method  of  saponifying  by  so- 
dium hydroxide  and  acidifying  with  normal  sulfuric  acid.  In  this  case 
the  sulfate  precipitates  instead  of  the  anhydride.  The  precipitate  is  at 
first  slimy  but  becomes  crystalline  on  standing.  It  can  be  crystallized 
from  alcohol  in  needles.  It  decomposes  slowly  at  180°  (CHHgS) .  It 
is  almost  insoluble  in  organic  solvents,  easily  soluble  in  hot  water.  The 
corresponding  chloride  is  obtained  from  the  saponification  mixture  by 
acidifying  with  normal  hydrochloric  acid  instead  of  sulfuric  acid.  On 
rapid  heating  it  melts  with  decomposition  at  175°.  It  is  very  easily 
soluble  in  boiling  water,  fairly  in  cold,  difficultly  soluble  in  most 
organic  solvents. 

The  diethyl  ester  of  o-carboxylphenylamino  acetic  acid  reacts  with 
mercuric  acetate  giving  only  a  mono  mercury  compound.33 
AcOHg  —  C6H3  (C02Et)  —  NH  —  CH2CO,Et, 

82  Ibid. 

83  J.  Bother,  Dissert.  Berlin,  1911,  pp.  18  and  53, 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      303 

Derivatives  of  acylated  m-aminobenzoic  acids.3* 

Heating  the  corresponding  mercury  salts  gives  the  anhydrides  of 
2-hydroxymercuri-5-acetaminobenzoic  acid,  and  the  corresponding  ben- 
zoylamino  compound. 

Derivatives  of  p-aminobenzoic  acid.55 

The  ethyl  ester  of  p-aminobenzoic  acid  reacts  with  mercuric  acetate 
in  methyl  alcohol  much  as  does  the  ester  of  anthranilic  acid.  It 
forms  the  corresponding  "N-isodiacetate."  This  changes  on  heating 
into  the  true  organic  di-acetoxymercuri  compound  but  differs  from 
the  anthranilic  compound  in  that  it  does  this  even  in  presence  of 
an  excess  of  the  original  ester.  Thus  in  the  case  of  the  p-compound 
further  mercuration  of  the  same  molecule  is  easier  than  the  transfer 
of  the  — HgOAc  group  to  a  molecule  of  unmercurated  ester  while 
the  reverse  is  true  in  the  case  of  the  ortho  compound.  This  conclu- 
sion may  be  erroneous  as  the  difference  might  be  due  to  the  difference 
between  the  methyl  and  ethyl  esters  used.  The  reaction  of  the  p-com- 
pound differs  also  in  that  an  excess  of  the  ester  gives  a  compound  in 
which  one  mercury  atom  is  linked  to  two  nitrogen  atoms  each  of  which 
has  a  molecule  of  acetic  acid  added  to  it  making  it  quinquevalent. 
This  compound  may  be  regarded  as  a  mercuric  acetate  "salt"  of  a 
mercurated  substituted  aniline, 

HgOAc  HgOAc 

TVTTT                       XTTT         /\       "Mercury-N-iso" 
—  NH0 Hg NH0—  (    >  ^ iL—j 


OAc  Oi 


Compound. 


Et02C—  I       1       OAc  OAc       I       1— C02Et. 

This  would  correspond  to  the  commonest  mercuric  "salt"  of  aniline, 
C6H5  —  NH2  -  Hg  —  NH2  -  C6H5 

Cl  Cl 

N-iso  diacetoxymercuri-p-aminobenzoic  ethyl  ester, 

AcOHg  —  C6H3  (C02Et)  —  NH  —  HgOAc. 

This  substance  is  obtained  as  a  yellow  amorphous  mass  by  allow- 
ing the  ethyl  ester  to  stand  with  2  moles  of  mercuric  acetate  in  methyl 
alcohol  for  a  day.  The  substance  cannot  be  recrystallized.  (CHNHg) . 

3"  D.  R.  P.  264,388.     Frankel,  668. 

35  Schoeller,  Schrauth,  and  Liese,  Ber.  52  (1919),  1782, 


304  COMPOUNDS  OF  MERCURY 

M.P.  about  245°.  It  is  soluble  in  ammonium  hydroxide,  acetic  acid, 
and  is  decomposed  by  mineral  acids.  It  is  practically  insoluble  in  or- 
ganic solvents.  It  reacts  in  the  cold  with  ammonium  sulfide.  The 
acetic  acid  solution  when  treated  with  sodium  chloride  loses  one-half 
of  its  mercury  as  mercuric  chloride  leaving  chloromercuri-p-aminoben- 
zoic  ester.  When  warmed  with  acetic  acid  it  gives  diacetoxymercuri- 
p-aminobenzoic  ethyl  ester,  (AcOHg)2C6H2(C02Et)  — NH2. 

This  reaction  takes  place  even  in  the  presence  of  an  excess  of  the 
free  ester  (contrast  the  o-compound).  If  boiled  with  methyl  alcohol 
and  acetic  acid  and  sodium  chloride  solution  it  gives  a  94%  yield  of 
chloromercuri-p-aminobenzoic  ester.  The  filtrate  when  treated  with 
ammonium  hydroxide  and  hydrogen  sulfide  gives  mercuric  sulfide  cor- 
responding to  one-half  of  the  mercury  in  the  original  compound.  An- 
other method  of  making  the  N-iso  di-acetoxymercuri  compound  is  to 
boil  the  mercuric  acetate  "salt"  with  methyl  alcohol.  This  precipitates 
the  N-isodiacetate  in  72%  yield.  The  latter  substance  when  treated 
with  sodium  chloride  solution  and  hydrogen  sulfide  loses  one-half  of 
its  mercury  as  mercuric  sulfide. 

Mercuric  acetate  salt  of  acetoxymercuri-p-aminobenzoic  ethyl  es- 
ter. ("Mercury-N-iso"  compound.  See  above  formula.) 

It  is  prepared  from  equivalent  amounts  of  the  ester  and  mercuric 
acetate  allowed  to  stand  in  methyl  alcohol.  It  forms  microscopic  dia- 
mond shaped  crystals.  M.P.  230-240°.  Analysis  (CHNHg,HOAc) 
distilled  off  over  phosphoric  acid  .  It  dissolves  in  ammonium  hydroxide 
and  acids  with  decomposition,  dissolves  a  little  in  cold  methyl  alcohol, 
acetone,  and  ethyl  acetate.  It  reacts  with  cold  ammonium  sulfide. 
Boiling  with  methyl  alcohol  gives  a  precipitate  of  the  "N-isodiace- 
tate" and  a  solution  of  acetoxymercuri-p-aminobenzoic  ethyl  ester. 
The  mother  liquor  contains  two  moles  of  acetic  acid. 

When  the  "Mercury-N-iso"  compound  is  boiled  with  acetic  acid 
and  then  heated  in  a  vacuum  to  drive  off  the  acetic  acid,  it  leaves  a 
residue  which  is  partly  soluble  in  methyl  alcohol.  The  methyl  alcohol 
solution  treated  with  sodium  chloride  gives  chloromercuri-p-amino- 
benzoic ethyl  ester.  The  insoluble  residue  is  extracted  with  ethyl  ace- 
tate giving  di-acetoxymercuri-p-aminobenzoic  ester.  The  final  insolu- 
ble portion  consists  of  traces  of  mercurous  acetate.  When  the  "Mer- 
cury-N-iso" compound  is  treated  with  methyl  alcohol,  acid  and  sodium 
chloride,  it  gives  chloromercuri-p-aminobenzoic  ester.  The  mother 
liquor  treated  with  ammonium  sulfide  gives  an  amount  of  mercuric 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      305 

sulfide  corresponding  to  one-third  of  the  mercury  originally  present  in 
the  compound. 

Acetoxymercuri-p-aminobenzoic  ethyl  ester.56 

It  is  prepared  from  equivalent  amounts  of  the  ester  and  mercuric 
acetate  in  warm  acetic  acid.  The  precipitate  formed  is  .extracted  with 
methyl  alcohol  which  dissolves  the  mono-mercurated  product  but 
leaves  the  di-product.  It  is  not  possible  to  get  the  mono  compound 
pure  by  carrying  out  the  reaction  in  acetic  acid  or  methyl  alcohol 
solution.  The  best  method  of  preparation  is  to  heat  equivalent 
amounts  of  the  ester  and  mercuric  acetate  without  any  solvent  in  a 
glycerine  bath.  At  130°  the  mixture  melts  and  at  a  higher  tempera- 
ture acetic  acid  is  given  off.  Finally  the  mixture  solidifies  to  a  cake 
at  160°.  This  is  cooled,  broken  up,  and  extracted  with  hot  methyl 
alcohol,  evaporated  and  diluted  with  hot  water.  The  acetate  forms 
beautiful  white  clustered  needles.  The  residue  insoluble  in  methyl 
alcohol,  is  a  partly  acetylated  di-acetoxymercuri  compound.  Analysis 
of  mono-ajcetate,  CHNHg.  It  melts  partly  at  182°,  solidifies  and 
again  melts  at  228°.  It  is  soluble  in  most  organic  solvents,  especially 
in  methyl  alcohol,  ethyl  acetate  and  chloroform.  It  is  also  soluble 
in  dilute  acetic  acid  and  slightly  in  water,  difficultly  soluble  in  ether 
and  low  boiling  ligroin.  It  is  stable  to  ammonium  sulfide  forming 
a  yellow  sulfide  which  blackens  only  on  long  boiling.  Another  prepa- 
ration is  that  already  mentioned  by  heating  the  "Mercury-N-iso" 
compound  with  methyl  alcohol.  If  the  acetate  is  boiled  with  sodium 
hydroxide  and  the  resulting  solution  is  acidified  there  results  the  an- 
hydride of  hydroxymercuri-p-aminobenzoic  acid. 

Chloromercuri-p-aminobenzoic  ethyl  ester. 

It  is  prepared  from  the  acetate  by  sodium  chloride.  M.P.  223°.  It 
is  difficultly  soluble  in  common  solvents.  It  is  best  purified  by  dis- 
solving in  ethyl  acetate,  and  adding  low  boiling  ligroin  in  which  it  is 
practically  insoluble.  (CHNClHg).  It  is  stable  to  ammonium  sulfide 
except  on  long  boiling.  The  chloride  can  also  be  prepared  by  boiling 
the  "N-iso"  or  the  "Mercury-N-iso"  compound  with  methyl  alcohol 
and  acetic  acid  and  precipitating  the  resulting  solution  with  sodium 
chloride. 

36  Schoeller,  Schrauth,  and  Liese,  Ber.  52    (1919),  1784. 


306  COMPOUNDS  OF  MERCURY 

Anhydride  of  hydroxymercuri-p-aminobenzoic  acid.37 

The  acetate  of  the  corresponding  ethyl  ester  is  suspended  in  water 
and  saponified  by  boiling  with  normal  sodium  hydroxide.  The  solu- 
tion of  the  sodium  salt  is  cooled  and  treated  with  a  slightly  more  than 
the  calculated  amount  of  the  normal  sulfuric  acid.  An  excess  of  acid 
will  dissolve  the  anhydride.  The  precipitate  formed  is  very  insoluble 
in  common  solvents.  It  is  soluble  in  ammonium  hydroxide.  This 
solution  reacts  with  ammonium  sulfide  only  on  heating.  It  is  soluble 
in  water  solutions  of  many  salts  such  as  sodium  thiosulfate,  potassium 
iodide  and  potassium  chloride.  It  is  also  soluble  in  bases  with  salt 
formation.  The  anhydride  has  also  been  obtained  by  mercurating 
the  isobutyl  ester  of  p-aminobenzoic  acid,  saponifying  the  product, 
and  acidifying.38 

Dwcetoxymercuri-p-aminobenzoic  ethyl  ester, 

(AcOHg)2C6H2(C02Et)  —  NH2. 

It  is  prepared  from  the  ester  and  two  molecules  of  mercuric  acetate 
in  acetic  acid.  After  standing  for  two  days  a  well  crystallized  product 
is  obtained.  The  pure  di-compound  is  obtained  by  washing  this 
precipitate  with  methyl  alcohol  and  ether.  It  is  only  slightly  soluble 
in  common  solvents,  but  can  be  recrystallized  from  acetone  or  ethyl 
acetate  in  flat  needles.  M.P.  255-7°.  The  diacetate  can  also  be  pre- 
pared by  boiling  the  "N-iso"  or  the  "Mercury-N-iso"  compound  with 
acetic  acid  and  diluting  the  solution.  It  is  stable  to  ammonium  sulfide 
even  on  gentle  warming.  (CHNHg).  It  can  be  acetylated  by  acetic 
acid  and  acetic  anhydride  forming  diacetoxymercuri-p-acetamino- 
benzoic  ethyl  ester. 

It  is  purified  by  recrystallization  from  dilute  alcohol  or  by  solution 
in  acetic  acid  and  dilution  with  hot  water.  Fine  needles.  (CHNHg) . 
M.P.  247°. 

Dichloromercuri-p-aminobenzoic  ethyl  ester. 

It  is  prepared  from  the  diacetate  dissolved  in  acetic  acid  and  methyl 
alcohol  and  precipitated  by  sodium  chloride.  Fine  needle  crystals  not 
very  soluble  in  ethyl  acetate,  soluble  in  acetone.  M.P.  270°  (CHHg). 

87  Ibid.  1785. 

88  D.  R.  P.  248,291.     Chem.  Zentr.  1912  II  211.     FriedlSnder,  10,  1278.     Frankel, 
662. 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      307 

3,  3'-Mercuribis-4-aminobenzoic  ethyl  ester.™ 

Chloromercuri-p-aminobenzoic  ethyl  ester  is  warmed  with  a  concen- 
trated solution  of  sodium  thiosulfate.  Most  of  the  substance  goes  into 
solution.  A  precipitate  soon  starts  to  form.  This  dissolves  well  in 
ethyl  acetate.  It  can  be  purified  by  dissolving  in  benzene  and  adding 
ligroin.  Slightly  yellow  needles.  M.P.  176°  corr.  (CHHg). 

2j  2'-Mercuribis-4-ciminobenzoic  acid.4"0 

Neutral  or  alkaline  reduction  of  the  anhydride  or  salts  of  the  hy- 
droxy-mercuri-p-nitrobenzoic  acid  obtained  by  heating  the  correspond- 
ing acid  with  mercuric  oxide  until  the  product  is  completely  soluble  in 
sodium  hydroxide,  gives  this  substance.  The  sodium  salt  is  a  yellow- 
ish white  crystalling  powder  which  is  readily  soluble  in  water.  The 
free  acid  is  precipitated  by  the  addition  of  dilute  hydrochloric  acid  to 
the  solution  of  the  sodium  salt.  Hydrogen  sulfide  gives  no  mercuric 
sulfide.  It  can  be  diazotized  and  coupled  with  an  acid  solution  of 
alpha  naphthylamine  or  with  basic  solutions  of  the  naphthols.  With 
the  former  it  gives  a  blue  violet  color  and  with  the  two  latter  purple 
red  solutions. 

Animal  experiments  with  salts  of  the  above  acid.41 

The  chart  on  page  308  will  illustrate  the  relations  between  the  mer- 
curation  products  of  the  aminobenzoic  acids. 

Toluidoacetic  esters.    See  under  Toluidine.42 

Sulfamido  benzole  compounds. 

The  sodium  compound  of  saccharin  43  reacts  with  mercuric  salts 
giving  N  -•-  Hg  compounds  of  saccharin.  These  compounds  react  with 
bases,  iodides,  and  sulfides  giving  the  characteristic  reactions  of  mer- 
curic ions. 

Salts  of  the  mono-  and  di-sulfamido  benzole  acids  react  with  mer- 
curic oxide  or  carbonate  giving  soluble  compounds  containing  the 
grouping,  —  S02  —  NH  —  HgOH.44 

s»Schoeller  and  Schrauth,  Ber.  53   (1920),  643. 

*>  Blumenthal,  Biochem.  Z.  32  (1911),  60.  Chem.  Atst.  6  (1912),  1466.  D.  R.  P. 
249,725.  Frankel,  670. 

«  Blumenthal  and  Oppenheim,  Biochem.  Z.  36  (1911),  295;  39  (1912),  53;  57 
(1913),  287. 

«J.  Bother,  loc.  cit.  42. 

*3Dufournel,  Bull.  soc.  chim.  (3)  25  (1901),  326.  Auld,  J.  Chem.  Soc.  91  (1907), 
1048. 

«*  D.  R.  P.  242,571  and  242,572.     Chem.  Zentr.  1912  I  385. 


308 


COMPOUNDS  OF  MERCURY 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      309 

These  compounds  react  with  ammonium  sulfide.  They  form  soluble 
compounds  with  2  molecules  of  mercurisalicyl  anhydride  for  each 
-  S02NH  —  Hg  —  HgOH  group. 

These  solutions  do  not  act  on  metals  or  albumen.  What  is  more 
remarkable  is  that  they  do  not  react  with  ammonium  sulfide  except 
on  boiling.45 

Benzosulfonic  acids.46 

Saccharine  reacts  with  mercuric  acetate  in  boiling  water  solution 
forming  a  mercury  compound  which  is  insoluble  in  acids  and  alkalies 
but  is  soluble  in  physiological  salt  solution.4651 

Hydroxymercuri  o-toluylic  acid47 

The  anhydride  is  obtained  in  the  usual  way  by  heating  the  acid 
with  mercuric  oxide  until  the  product  is  alkali  soluble. 

Anhydride  of  a-hydroxymercuri-fi-phenyl  propionic  acid47* 
C6H5  —  CH2  —  CH  —  C  =0 


The  mercuric  salt  of  benzylmalonic  acid  is  heated  to  drive  out  one 
molecule  of  carbon  dioxide.  Treatment  of  the  anhydride  with  the  cal- 
culated amount  of  hydrochloric  acid  gives  the  a-chloromercuri  com- 
pound. 

Anhydride  of  2-hydroxymercwri-S,  6-dimethylbenzoic  acid48 
Anhydride  of  2-hydroxymercuri  trimethylbenzoic  acid49 

Mercury  Derivatives  of  Cinnamic  Acid  and  Its  Esters. 

Common  cinnamic  acid  gives  no  compound  with  mercuric  salts 
from  which  all  of  the  mercury  cannot  be  precipitated  by  bases.  Allo- 
cinnamic  acid,  however,  reacts  readily  giving  an  anhydride  in  which 
the  mercury  is  so  attached  that  it  is  not  precipitated  by  bases.50 

«  D.  R.  P.  247,625.     Chem.  Zentr.  1912  II  166. 

*«D.  R.  P.  281,009.     Chem.  Zentr.  1915  I  73.     Frankel,  670. 

46a  private  communication,  G.   W.   Raiziss. 

*7D.  R.  P.  234,054.  Frankel,  6G5.  D.  R.  P.  234,914.  Chem.  Zentr.  1911  II  112. 
Chem.  Abst.  6  (1912),  2674.  D.  R.  P.  286,977.  Chem.  Abst.  10  (1916),  1694.  Bech- 
hold,  Chem.  Zentr.  1915  I  562. 

4?a  private  communication,  M.  S.  Kharasch. 

48  D.  R.  P.  249,332.     Chem.  Zentr.  1912  II  46.r».     Chem.  Alst.  6  (1912),  2674. 

«•  Hid. 

wBiilmann,  Ber.  35  (1902),  2576;  43  (1910),  574. 


310  COMPOUNDS  OF  MEftOURY 

Anhydride  of  a-hydroxymercuri-fi-hydroxyhydrocinnamic  acid,5i 
C6H5  —  CH  —  CH  —  C  =  0. 

OH      Hg  — 0 

It  is  prepared  by  treating  allocinnamic  acid  at  100°  with  a  hot  so- 
lution of  mercuric  acetate,  formed  from  mercuric  oxide  and  dilute 
acetic  acid.  White  microscopic  crystals.  Yield  2.3  gm.  from  1  gm. 
of  the  acid. 

It  is  neutral.  It  is  soluble  in  bases,  soluble  in  carbonates  only  on 
heating.  Ammonium  hydroxide  hardly  attacks  it.  No  reaction  is 
obtained  at  first  with  alkaline  sulfide  solution,  black  mercuric  sulfide 
on  standing.  Potassium  iodide  gives  a  clear  alkaline  solution.  It  is 
only  slightly  soluble  in  organic  solvents.  The  anhydride  can  be  dis- 
solved in  alkali  and  reprecipitated  by  carbon  dioxide.  The  reprecipi- 
tated  substance,  however,  has  a  considerably  larger  per  cent  of  mer- 
cury and  a  smaller  per  cent  of  carbon.  If  the  anhydride  is  dissolved 
in  normal  sodium  hydroxide  and  the  solution  is  saturated  with  hy- 
drogen sulfide  and  ammonium  sulfate  is  added  to  completely  precipi- 
tate the  mercuric  sulfide  a  solution  is  obtained  from  which  an  80  per 
cent  yield  of  phenyl  hydracrylic  acid  can  be  extracted.  M.P.  91° 
(Lit.  93°).  (Carbon  and  hydrogen  analyses  for  C9H1003.)  Boiling 
the  hydracrylic  acid  with  dilute  acid  gives  common  cinnamic  acid, 
M.P.  133°.  If  the  anhydride  is  heated  with  hydrochloric  acid  it  is 
easily  changed  to  mercuric  chloride  and  common  cinnamic  acid.  The 
primary  product  of  the  splitting  by  acid  must  be  phenyl  hydracrylic 
acid  because  allocinnamic  acid  is  not  changed  to  common  cinnamic 
acid  by  boiling  with  HC1  or  with  HC1  and  mercuric  chloride.  This 
plausible  proof  that  the  splitting  of  the  C  —  Hg  bond  by  acid  pre- 
cedes any  action  of  the  —  OH  group  is  of  importance  in  the  theories 
about  mercuration  of  double  bond  compounds.  The  fact  that  the  salts 
of  the  so-called  a-hydroxymercuri-(3-hydroxy  ethane  react  with  acids 
giving  ethylene  has  been  explained  by  assuming  that  the  hydroxyl 
group  on  the  carbon  alpha  to  the  C  —  Hg  linkage .  is  unusually  re- 
active and  is  replaced  by  chlorine  when  treated  with  HC1,  even  di- 
lute. This  would  give  a  compound,  Cl  —  CH2  —  CH2  —  HgCl,  which 
is  apparently  incapable  of  existence  and  therefore  loses  HgCl2  leaving 
ethylene.  If,  as  the  work  with  the  mercurated  cinnamic  acid  indicates, 
the  C  —  Hg  is  first  attacked  this  explanation  is  weakened  and  the  idea 

51  Biilmann,  loc.  cit.  2571  and  575. 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      311 

that  the  ethylene  mercuric  compounds  are  not  true  "structure"  com- 
pounds is  strengthened. 

Compounds  derived  from  the  mercuration  of  cinnamic  esters  in  alcohol 

solution.52 

Cinnamic  esters  react  with  mercuric  acetate  in  alcohol  solution  in 
such  a  way  that  the  groups  — HgOAc  and  — OR  are  added  to  the 
unsaturated  carbon  atoms  respectively,  forming  compounds, 

C6H5  —  CH  —  CH  —  C02R'. 


OR      Hi 


[gOAc 

The  reaction  has  been  carried  out  in  the  following  alcohols,  methyl, 
ethyl,  n-propyl,  i-propyl,  and  i-butyl.  The  reaction  in  n-butyl  alco- 
hol and  in  higher  and  in  poly  alcohols  gives  no  satisfactory  results. 
When  these  esters  are  saponified  and  then  acidified  the  anhydrides  of 
the  corresponding  pi-hydroxymercuri-p-alkoxy  hydrocinnamic  acids 
are  obtained,  C6H5  —  CH  (OR)  —  CH  —  C  =0.  When  these  anhy- 


L-A 


drides  are  dissolved  in  bases  and  treated  with  hydrogen  sulfide  the 
C  —  Hg  bond  is  broken  and  the  corresponding  (3-alkoxy  hydrocinnamic 
acids  are  obtained,  C6H5  —  CH  (OR)  —  CH2  —  C02H. 

Mercuration  in  methyl  alcohol. 
a-Acetoxymercuri-fi-methoxy  hydrocinnamic  methyl  ester.53 

Dry  mercuric  acetate  is  dissolved  in  warm  methyl  alcohol  and 
mixed  with  one  mole  of  methyl  cinnamate.  Crystals  appear  in  four 
hours  and  the  reaction  is  complete  in  six,  (NaOH  test) .  After  stand- 
ing two  days  a  65  per  cent  yield  of  crystals  separates.  The  rest  of 
the  mercurated  product  may  be  obtained  by  evaporation  or  by  treating 
the  mother  liquids  with  sodium  chloride  solution.  The  product  is  dis- 
solved in  ethyl  acetate  and  precipitated  by  adding  low  boiling  ligroin. 
M.P.  139°  (corr.  140.5°)  (CHHg).  It  is  easily  soluble  even  in  the 
cold  in  alcohol,  ethyl  acetate,  acetone  and  most  organic  solvents.  It 
forms  small  needles  from  ethyl  acetate  and  ligroin,  which  on  stand- 
ing several  days  grow  to  blunt  transparent  prisms  a  centimeter  long 

82  Schoeller,  Schrauth,  and  Struensee,  Ber.  43  (1910),  695;  44  (1911),  1432;  44 
(1911),  1048.  D.  R.  P.  228,877.  Frankel,  666. 

"Schoeller,  Schrauth,  and  Struensee,  Ber.  43  (1910),  695. 


312  COMPOUNDS  OF  MERCURY 

and  several  millimeters  thick.  When  the  ester  is  heated  with  slightly 
over  two  equivalents  of  normal  base  it  dissolves.  Addition  of  one 
equivalent  of  normal  acid  causes  a  white  flocculent  precipitate  of  the 
anhydride.  The  ester  dissolved  in  warm  alcohol  and  treated  with  am- 
monia gas  and  then  with  hydrogen  sulfide  gives  mercuric  sulfide.  The 
filtrate  gives  an  oil  which  distills  at  248°  (corr.  253°)  and  gives  car- 
bon and  hydrogen  analyses  corresponding  to  (3-methoxy  hydrocinnamic 
methyl  ester. 

Halidemercuri  fi-methoxy  hydrocinnamic  methyl  esters.54' 

The  chloride  is  prepared  from  the  acetate.  It  crystallizes  from 
ethyl  acetate  in  short  needles.  M.P.  132.5°  (corr.  133.5°)  (CIHgCH). 

Bromide.  Needle  crystals.  M.P.  110.5°  (BrHg).  Iodide.  Needles. 
M.P.  100°  (IHg). 

A  veronal  compound  is  obtained  by  treating  the  acetate  with  sodium 
diethyl  barbiturate.  (NHg) . 

a-Actoxymercuri-fi-methoxy  hydrocinnamic  ethyl  ester.55 

This  compound  is  prepared  from  ethyl  cinnamate  in  methyl  alcohol 
and  a  concentrated  aqueous  solution  of  one  mole  of  mercuric  acetate. 
In  this  case  the  solution  is  much  less  rapid.  The  sodium  hydroxide 
test  does  not  fail  until  the  mixture  has  stood  for  24  hours  (6  in  case  of 
the  methyl  ester) .  Crystals  do  not  begin  to  form  for  three  days  and  the 
mixture  is  not  filtered  for  twelve.  This  difference  in  the  velocities 
of  the  reaction  may  be  due  to  a  difference  between  the  reactivity  of 
the  two  esters  or  to  the  fact  that  water  was  used  in  one  case  and  not 
in  the  other  or  to  both  of  these  facts.  Yield  45  per  cent.  The  product 
crystallizes  from  ethyl  acetate  in  small  transparent  prisms.  Very 
soluble  in  organic  solvents.  M.P.  107°  (Hg). 

(y-Chloromercuri-fi-methoxypropyl)a-chloromercuri-fi-methoxyhydro- 

cinnamate*6 
C6H5  -  CH  (OMe)  -  CH  (HgCl)  -  C02CH2  -  CH  (OMe)  -  CH2HgCl. 

Allyl  cinnamate  is  treated  with  two  moles  of  mercuric  acetate  in 
absolute  methyl  alcohol.  The  reaction  is  complete  in  a  few  hours.  No 
crystals  separate  even  on  long  standing.  The  solution  is  treated  with 
sodium  chloride  solution.  An  oily  precipitate  settles  which  finally 

M  IMd.  697. 

"Schoeller,  Schrauth,  and  Struensee,  Ber.  44   (1911),  1054. 

"Schrauth  and  Schoeller,  Ber.  44  (1911),  1055. 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      313 

changes  to  white  crystals.  These  are  recrystallized  from  hot  absolute 
alcohol.  White  needles.  M.P.  169°,  gas.  It  is  easily  soluble  in  alco- 
hol, chloroform,  benzene,  ethyl  acetate,  easily  soluble  in  sodium  hy- 
droxide. Sulfuric  acid  gives  a  white  flocculent  precipitate.  (ClHg) . 

a-Acetoxymercuri-fi-methoxy  hydrocinnamic  benzyl  ester.57 

Benzyl  cinnamate  treated  with  methyl  alcohol  and  mercuric  acetate 
gives  a  50  per  cent  yield  of  crystals  on  standing  a  few  days.  Crystal- 
lizes from  ethyl  acetate  in  colorless  silky  needles.  M.P.  127°  (Hg). 

Anhydride  of  a-hydroxymercuri-fi-methoxy  hydrocinnamic  acid.58 

The  corresponding  methyl  ester  is  heated  with  slightly  more  than 
two  equivalents  of  normal  sodium  hydroxide  until  dissolved  and  then 
neutralized  with  normal  sulfuric  acid.  A  white  flocculent  precipitate 
is  formed.  This  is  pure.  It  can  be  dissolved  in  ethyl  acetate  and  pre- 
cipitated by  adding  low  boiling  ligroin.  (CHHg).  It  decomposes  about 
184°  (corr.  187°).  The  solution  in  ammonium  hydroxide  gives  mer- 
curic sulfide  at  once  with  ammonium  sulfide.  Its  solution  in  alkalies 
gives  precipitates  with  solutions  of  heavy  metal  salts. 

Methoxy  hydrocinnamic  acid  may  be  obtained  from  the  mercury 
compound.  The  hydroxide  is  dissolved  in  normal  sodium  hydroxide 
solution  and  saturated  with  hydrogen  sulfide.  Then  an  excess  of  solid 
ammonium  sulfate  is  added  to  insure  the  complete  precipitation  of  the 
mercuric  sulfide.  The  filtrate  is  barely  acidified  with  normal  sulfuric 
acid  and  treated  with  a  stream  of  air  to  remove  all  hydrogen  sulfide. 
A  white  crystalline  precipitate  is  formed.  The  mixture  is  extracted 
repeatedly  with  ether.  The  ether  is  evaporated  and  the  residue  is 
crystallized  from  hot  ligroin.  Thick  transparent  colorless  plates  sepa- 
rate in  84  per  cent  yield.  The  product  gives  carbon  and  hydrogen 
analyses  for  |3-methoxy  hydrocinnamic  acid. 

a-Mercuri-di-fi-phenyl-anhydrohydracrylic  acid, 
C6H5  —  CH  —  CH  —  CO2H. 

0         Hg 

C6H,  —  CH  —  CH  —  CO2H 

The  anhydride  of  a-hydroxymercuri-(3-methoxy  hydrocinnamic 
acid  treated  with  alcohol  and  an  aqueous  solution  of  potassium  iodide 

"/bid.  1055. 

"Schoeller,  Schrauth,  and  Struensee,  Per.  43  (1910),  697. 


314  COMPOUNDS  OF  MERCURY 

gives  a  solution  from  which  normal  sulfuric  acid  precipitates  a  white 
flocculent  compound  contaminated  by  a  little  mercuric  iodide.  The 
latter  is  removed  by  washing  with  potassium  iodide  solution.  The  yield 
is  ten  per  cent  of  the  weight  of  anhydride  used.  The  substance  can  be 
recrystallized  from  alcohol  in  which  it  is  slightly  soluble.  It  forms 
white  shining  rhombic  leaflets.  It  melts  and  decomposes  at  200°.  It  is 
practically  insoluble  in  organic  solvents  but  easily  soluble  in  alkalies.  It 
neutralizes  two  equivalents  of  sodium  hydroxide  with  phenolphthalein 
as  indicator.  (CHHg).  The  solution  in  ammonium  hydroxide  treated 
with  ammonium  sulfide  gives  no  mercuric  sulfide  even  on  long  boiling. 
Long  boiling  with  concentrated  hydrochloric  or  nitric  acid  gives  mer- 
curic ions.  The  other  product  is  not  mentioned. 

Mercuration  in  Ethyl  Alcohol52 
a-Acetoxymercuri-fi-ethoxy  hydrocinnamic  methyl  ester. 

Methyl  cinnamate  reacts  slowly  with  mercury  acetate  in  ethyl  alco- 
hol (better  not  absolute).  After  several  days  a  30  per  cent  yield  of 
crystals  is  obtained.  More  material  can  be  obtained  from  the  mother 
liquor  by  adding  sodium  chloride.  It  is  very  soluble  in  organic  sol- 
vents. It  is  best  recrystallized  from  ethyl  acetate.  M.P.  122.5°  (corr. 
123°)  (CHHg) .  When  the  ester  is  treated  with  alcoholic  ammonia  and 
hydrogen  sulfide  the  C  —  Hg  bond  is  broken  and  p-ethoxy  hydrocin- 
namic methyl  ester  is  obtained  as  a  liquid  boiling  at  251°  (corr.  256°). 
Yield  75  per  cent.  (CH).  Treated  with  sodium  hydroxide  and  sulfuric 
acid  it  forms  the  anhydride  of  a-hydroxymercuri-|3-ethoxy  hydrocin- 
namic acid. 

a-Halidemercuri-fi-ethoxy  hydrocinnamic  methyl  esters. 

The  Chloride  is  prepared  from  the  acetate  in  the  usual  way  and 
crystallizes  from  ethyl  acetate  in  fine  needles.  M.P.  114°  (Hg). 

Bromide.    Small  white  needles.    M.P.  85°   (Hg). 

The  iodide  is  hard  to  crystallize.  M.P.  71°.  It  is  discolored  on 
standing.  (No  analysis.) 

Anhydride  of  a-hydroxymercuri-fi-ethoxy  hydrocinnamic  acid. 

It  is  prepared  in  the  usual  way  from  the  acetate.  It  decomposes  at 
about  188°  (corr.  191°)  with  evolution  of  gas.  (CHHg).  When  treated 
with  sodium  hydroxide  and  hydrogen  sulfide,  it  gives  p-ethoxy  hy- 
drocinnamic acid  in  96  per  cent  yield.  (CH). 

»  Schoeller,  Schrauth,  and  Struensee,  loc.  cit.  698  and  1434. 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      315 

When  this  acid  is  boiled  a  short  time  with  hydrochloric  acid  it  gives 
common  cinnamic  acid  (M.P.  133°)  and  ethyl  alcohol  which  is  identi- 
fied by  the  iodoform  test. 

Mercuration  in  n-Propyl  Alcohol. 
a-Acetoxymercuri-fi-n-propoxy  hydrocinnamic  methyl  ester. 

The  reaction  of  methyl  cinnamate  with  mercuric  acetate  in  n-propyl 
alcohol  containing  a  few  drops  of  acetic  acid  is  complete  only  after  sev- 
eral days.  In  two  weeks  a  71  per  cent  yield  of  crystals  forms.  These 
are  recrystallized  from  ethyl  acetate.  Felted  needles.  M.P.  134.5° 
(corr.  135.5°).  It  is  very  soluble  in  organic  solvents.  (CHHg).  The 
corresponding  halides  are  easily  obtained  by  double  decomposition. 
All  are  purified  by  dissolving  in  ethyl  acetate  and  adding  ligroin. 
Chloride  M.P.  109°  (Hg),  Bromide  M.P.  84°  (Kg),  Iodide  M.P.  84° 
(Hg).  The  anhydride  is  prepared  in  the  usual  way.  It  decomposes 
about  185°  (corr.  188°)  (CHHg).  The  anhydride  yields  |3-n-propoxy 
hydrocinnamic  acid  melting  at  59°  (CH) . 

Mercuration  in  i-Propyl  Alcohol. 
a-Acetoxymercuri-fi-i-propoxy  hydrocinnamic  methyl  ester. 

The  reaction  runs  about  the  same  as  in  normal  propyl  alcohol. 
Solution  in  ethyl  acetate  leaves  some  mercurous  acetate  undissolved. 
M.P.  148°  (corr.  150°)  (CHHg).  The  halides  have  been  made  but 
not  studied.  The  anhydride  is  made  as  usual.  Yield  87  per  cent.  It 
decomposes  about  188°  (corr.  191°)  (CHHg).  When  the  anhydride  is 
decomposed  in  alkaline  solution  by  sulfides  it  gives  a  53  per  cent 
yield  of  (3-i-propoxy  hydrocinnamic  acid,  M.P.  73°  (CH). 

Mercuration  in  Isobutyl  Alcohol. 
a-Acetoxymercuri-fi-i-butoxy  hydrocinnamic  methyl  ester. 

Methyl  cinnamate  dissolved  in  isobutyl  alcohol  is  treated  with  a 
concentrated  solution  of  mercuric  acetate  in  warm  water  containing 
a  few  drops  of  acetic  acid  to  prevent  the  formation  of  mercuric  oxide. 
The  reaction  is  complete  in  8  days.  A  35  per  cent  yield  of  crystals  is 
obtained  in  17  days.  Some  mercurous  acetate  is  formed.  It  is  puri- 
fied by  ethyl  acetate  in  the  usual  way.  (CHHg).  M.P.  152°  (corr. 
154°).  The  halides  have  not  been  made.  The  anhydride  is  made  in 
the  usual  way.  Yield  94  per  cent.  It  decomposes  about  190°  (corr. 


316  COMPOUNDS  OF  MERCURY 

193°)   (CHHg).    The  anhydride  gives  the  corresponding  (3-alkoxy  hy- 
drocinnamic  acid  in  92  per  cent  yield.    M.P.  67.5°  (CH). 

Phenyl  propiolic  esters  are  said  to  react  with  mercuric  acetate  in 
alcohol  solution  in  the  same  way  as  cinnamic  esters. 

Mercury  Derivatives  of  Salicylic  Acids.60 

When  mercuric  salicylate  is  heated  to  about  100°  it  changes  to  the 
substance  known  as  "basic  mercury  salicylate"  which  is  really  a 
C  —  Hg  compound  or  a  mixture  of  such  compounds.  The  chief  con- 
stituents of  the  mixture  is  the  anhydride  of  3-hydroxymercuri-2-hy- 
droxybenzoic  acid.  Other  constituents  are  the  anhydride  of  the  cor- 
responding 5-hydroxymercuric  compound  and  the  anhydride  of  3-hy- 
droxymercuri-5-salicylatemercuri-2-hydroxybenzoic  acid. 

Anhydride  of  3-hydroxymercuri-2-hydroxybenzoic  acid. 

It  is  prepared  by  boiling  salicylic  acid  with  mercuric  oxide.  It 
forms  a  fine  white  powder  completely  soluble  in  sodium  hydroxide,  in- 
soluble in  water  and  all  organic  solvents.  The  solution  in  sodium  car- 
bonate or  sodium  hydroxide  is  precipitated  by  carbon  dioxide.  It  de- 
composes on  heating.  (CHHg).  It  is  soluble  in  sodium  chloride  so- 
lution forming  the  sodium  salt  of  chloromercurisalicylic  acid.  Hydro- 
gen sulfide  and  ammonium  sulfide  react  only  on  heating.  Treatment 
with  iodine  gives  o-iodosalicylic  acid.  Dilute  acid  splits  inorganic 
mercury  from  the  anhydride.  When  solid  mercuric  salicylate  is  heated 
above  100°  it  forms  salicylic  acid  and  the  C  —  Hg  anhydride.  The 
free  acid  can  be  washed  out  with  alcohol  and  ether.  The  change 
to  the  C  —  Hg  compound  takes  place  more  easily  than  in  the  unsub- 
stituted  benzoic  acid.  Mercuric  benzoate  must  be  heated  to  170°  to 
cause  the  mercury  to  replace  hydrogen  of  the  nucleus. 

3-Halidemercuri-£-hydroxy  benzoic  acids.61 

These  are  obtained  by  treating  the  anhydride  with  alkali  halides  and 
adding  dilute  acetic  acid  to  precipitate  the  free  acid  from  the  solution 
of  the  alkali  salt  first  formed.  They  are  obtained  as  gelatinous  pre- 
cipitates which  become  crystalline  on  standing.  They  are  slightly 

80Buroni,  Qazz.  chim.  ital.  32  II  (1902),  305.  Chem.  Zentr.  1903  I  578.  Diraroth, 
Ber.  35  (1902),  2033,  2873.  Brieger,  Aroh.  Pharm.  250  (1912),  62.  Chem.  Zentr. 
1912  I  753.  Gadamer,  Arch.  Ptwrm.  256  (1919),  263.  Chem.  Abst.  13  (1919),  1364. 

81  Buroni,  loc.  cit.  310. 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      317 

soluble  in  alcohol.  Metallic  salts  of  the  hydroxymercuri  salicylic 
acid  are  obtained  by  dissolving  the  anhydride  in  aqueous  or  alcoholic 
alkali  and  evaporating  the  solution  to  crystallization  in  a  vacuum. 

3,8'-Mercuribis-2-hydroxy  benzoic  acid.62 

It  is  prepared  by  a  neutral  reduction  of  the  anhydride.  The  heavy 
white  powder  is  insoluble  in  water.  It  is  decomposed  by  heat.  It  gives 
soluble  neutral  alkali  salts. 

Mercury  acetyl  salicylate.63 

When  the  mercuric  salt  of  acetylsalicylic  acid  is  heated  for  some 
time  at  about  100°  it  changes  to  a  glassy  mass  which  does  not  give 
mercury  reactions  with  sodium  hydroxide  or  ammonium  sulfide. 

Acetoxymercuri  salicylic  methyl  ester.6* 

It  is  prepared  by  heating  mercuric  acetate  with  methyl  salicylate 
and  a  small  amount  of  acetic  acid  for  40  minutes.  Crystals  separate 
on  cooling.  Yield  52  per  cent.  It  is  dissolved  in  hot  ethyl  acetate 
and  precipitated  by  adding  low  boiling  ligroin.  (CHHg) .  M.P.  202° 
(corr.),  after  slight  sintering.  It  dissolves  easily  in  warm  methyl 
and  ethyl  alcohols,  in  ethyl  acetate,  acetone,  and  chloroform.  It 
is  difficultly  soluble  in  water.  Alkalies  dissolve  it  with  saponification 
of  the  ester.  It  is  fairly  stable  to  ammonium  sulfide  but  less  so  than 
the  corresponding  mercurated  benzoic  ester.  It  is  easily  decomposed 
by  halogen  acids. 

C hloromercuri  salicylic  methyl  ester. 

The  mother  liquor  from  the  acetate  is  treated  with  sodium  chloride. 
It  is  purified  by  dissolving  in  ethyl  acetate  and  adding  low  boiling 
ligroin.  (CHHgCl).  It  is  less  soluble  in  alcohol  and  other  organic 
solvents  than  the  acetate.  It  is  fairly  stable  to  ammonium  sulfide 
but  less  so  than  the  benzoic  compound. 

Sulfidemercuri  salicylic  methyl  ester. 

It  is  prepared  from  a  cold  methyl  alcohol  solution  of  the  acetate 
treated  with  the  calculated  amount  of  an  alcoholic  solution  of  hydro- 
gen sulfide.  The  amorphous  white  precipitate  is  filtered  off.  Yield  85 
per  cent.  If  allowed  to  stand  in  the  mother  liquor  it  turns  yellow. 

62  D.  R.  P.  255,030.     Chem.  Zentr.  1913  I  248. 
^Gerngross  and  Kersasp,  Ann.  406  (1914),  248. 
"Schoeller  and  Schrauth,  Ber.  53  (1920),  639. 


318  COMPOUNDS  OF  MERCURY 

(S  Hg) .  It  is  soluble  in  chloroform,  benzene,  and  aniline,  soluble  in 
dilute  alkalies  and  alkali  sulfides.  It  has  no  definite  melting  point. 
When  the  sulphide  is  warmed  for  a  short  time  with  dilute  nitric  acid  a 
precipitate  of  mercuric  sulfide  is  formed.  This  contains  all  of  the 
sulphur  and  half  of  the  mercury  in  the  original  sulfide. 

Mercuribis-salicylic  methyl  ester. 

The  sulfide  is  heated  -at  110°  for  6  hours.  The  black  residue  is 
powdered  and  extracted  with  ethyl  acetate  giving  a  12  per  cent  yield 
of  the  R2Hg  compound.  It  is  better  prepared  by  the  action  of  sodium 
thiosulfate  on  the  acetate.  (CHHg).  It  is  easily  soluble  in  methyl  and 
ethyl  alcohol,  acetone,  ethyl  acetate,  chloroform,  and  benzene.  Diffi- 
cultly soluble  in  ether  and  low  boiling  ligroin.  M.P.  178-80°. 

Acetoxymercuri  salicylic  ethyl  ester.65 

Ethyl  salicylate  is  heated  to  180°  in  a  glycerine  bath  and  treated 
with  finely  powdered  mercuric  acetate  in  small  portions.  The  amor- 
phous brown  product  dissolves  on  further  heating.  When  no  mercuric 
ions  are  present  the  solution  is  cooled.  An  almost  quantitative  yield 
of  crystals  is  obtained.  It  recrystallizes  from  ligroin  and  ethyl  ace- 
tate. (CHHg).  It  sinters  at  200°  and  melts  at  206°  (corr.).  Its  solu- 
bilities are  like  those  of  the  methyl  ester. 

Mercuribis-salicylic  ethyl  ester. 

The  acetate  is  powdered  and  dissolved  in  cold  saturated  sodium  thio- 
sulfate. An  amorphous  precipitate  separates  almost  immediately.  The 
mother  liquor  gives  an  amount  of  mercuric  sulfide  with  ammonium 
sulfide  corresponding  to  almost  exactly  one-half  of  the  mercury  in  the 
original  compound.  Yield  82  per  cent.  The  impure  substance  is 
dried  in  a  vacuum  and  extracted  with  acetone  and  recrystallized  from 
ether.  (CHHg).  Its  solubilities  are  like  those  of  the  methyl  ester. 
M.P.  193°  (corr.). 

Water  soluble  compounds  of  mercuri  salicylic  anhydride.™ 

The  insoluble  anhydride  unites  with  a  great  variety  of  organic  sub- 
stances forming  water  soluble  compounds.  Among  the  substances 

83  lUd.  641. 

G6Buchtala,  Z.  physiol.  Chcm.  83  (1913),  280,  283.  Schoeller  and  Schrauth.  Therap. 
Monatsch.  23  (1909),  4.  Chem.  Zentr.  1910  I  948.  Chem.  Zentr.  1910  II  609.  Chem. 
Abst.  5  (1911),  156;  Ger.  Pat.  224,435.  Chem.  Zentr.  1910  II  701;  Ger.  Pat.  224,864. 
Chem.  Zentr.  1910  II  1423.  Chem.  Abst.  5  (1911),  2154;  Ger.  Pat.  227,391.  Engel- 
mann,  Chem.  Abst.  5  (1911),  971;  U.  S.  Pat.  978,145.  Bayer  &  Co.,  Chem.  Abst.  5 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      310 

which  form  these  compounds  are  sodium  (3-amino-a-oxyisobutyrate, 
sodium  diethyl  barbiturate,  sodium-a-amino  isobutyrate,  piperazine, 
various  acid  imides,  parabanic  acid,  acid  ureides  in  general,  urea,  di- 
cyandiamide,  urethanes,  nucleic  acids,  albumens,  xanthine  bases,  and 
mercury  compounds  of  sulfamidobenzoic  acids  containing  the  group, 
-S02  —  NH  —  HgOH. 

3-Acetoxymercuri-$-nitro-salicylic  acid  is  obtained  from  5-nitrosali- 
cylic  acid  and  mercuric  acetate  in  water  solution.6621  The  correspond- 
ing chloride  is  obtained  by  boiling  5-nitrosalicylic  acid  with  fresh 
mercuric  oxide,  dissolving  the  product  in  alkali,  and  precipitating  the 
solution  with  dilute  hydrochloric  acid.  (NHg)  .66a 

3,  5-Dinitrosalicylic  acid  reacts  with  a  boiling  water  solution  of  mer- 
curic acetate  giving  an  organic  mercury  compound  the  structure  of 
which  has  not  been  determined.6651  The  chloride  has  been  made 
(NClHg). 

5-Aminosalicylic  acid  reacts  with  mercuric  acetate  in  water  solution 
giving  an  acetoxymercuri  compound.  The  position  of  the  mercury  is 
not  known.664  The  corresponding  chloride  has  been  prepared. 

5-Acetaminosalicylic  acid  when  heated  with  fresh  mercuric  oxide  gives 
a  hydroxymercuri  compound.  (NHg)  .66a  Its  structure  is  not  known. 
The  chloride  has  been  prepared. 

3-Bromo-5-nitro-salicylic  acid  gives  an  acetoxymercuri  compound  of 
unknown  structure,  when  heated  with  mercuric  acetate  in  water  solu- 
tion.6fia 

2-Mercuri-5-hydroxy-benzoic  acid  compounds.^ 

The  anhydride  is  prepared  by  boiling  the  mercuric  salt  of  m-hy- 
droxy  benzoic  acid.  The  anhydride  gives  water  soluble  compounds 
when  treated  with  acetamide,  and  a  great  variety  of  organic  nitrogen 
compounds.  Most  important  of  these  are  veronal  (barbital)  and  alpha 
amino  acids. 

(1911),  3880;  U.  S.  Pat.  1,001,829.  Schoeller  and  Schrauth,  Biochem  Z  33  (1911) 
381.  Chem.  Zentr.  1911  II  707.  Chem.  Zentr.  1911  I  275-6-  Ger  Pats  229574 
229,575,  229,781.  Buchtala,  Z.  physiol.  Chem.  83  (1913),  249.  Blumenthal'  Biochem 
Z.  57  (1913),  261.  Chem.  Zentr.  1914  I  137.  Schmidt.  Pharm  Z  60  (1916)  724- 
Chem.  Abst.  10  (1916).  951.  D.  R.  P.  224,864.  Chem.  Zentr.  1910  II  701  D'R  p' 
247,625.  Frankel,  668.  Schmidt,  Pharmazeutische  Chem.  II  1180.  Frankel,  662 

•«*  Private  communication,   G.  W.  Raiziss. 

87  D.  R.  P.  229,575.     Chem.  Zentr.   1911  I  276.     D.   R.  P.  229  781       Ibid      Eneel 
mann,  Chem.  Alst.  7  (1913),  2094.     Lajouz,  Chem.  Atst.  9   (1915),  2527. 


320  COMPOUNDS  OF  MERCURY 

%-Mercuri-4-hydroxy-benzoic  acid  compounds.68 

When  the  mercuric  salt  of  p-hydroxy  benzole  acid  is  heated  com- 
plex basic  salts  are  said  to  be  obtained.  The  product  probably  contains 
C  —  Hg  compounds. 

2,  2'-Mercuribis-4-hydroxy-benzoic  acid.69 

The  corresponding  amino  compound  is  diazotized,  boiled  with 
water,  dissolved  in  sodium  hydroxide  and  precipitated  by  acetic  acid. 

3-Hydroxymercuri-2-hydroxy-5-sulfobenzoic  acid.70 

It  is  prepared  in  the  usual  way  from  the  acid  heated  with  mer- 
curic compounds.  It  is  soluble  in  water  but  insoluble  in  organic  sol- 
vents. Ammonium  sulfide  gives  a  dark  color  but  no  precipitate.  Alka- 
line or  neutral  reduction  gives  the  R2Hg  compound,  3-Mercuribis-2- 
hydroxy-5-sulfobenzoic  acid. 

3-Hydroxymercuri-4-hydrdxy-5-carboxyl  phenyl  arsonic  acid.71 

It  is  prepared  in  the  same  way  as  the  corresponding  sulfonic  acid. 
Alkaline  or  neutral  reduction  gives  the  R2Hg  compound. 

Mercury  Derivatives  of  Methoxybenzoic  Acids. 

Anhydride  of  3-hydroxymercuri-6-methoxybenzoic  acid72 

It  is  prepared  by  heating  a  paste  of  o-methoxybenzoie  acid  and 
mercuric  acetate  and  water  on  the  steam  bath.  It  is  soluble  in  chloro- 
form, insoluble  in  sodium  hydroxide.  This  insolubility  is  unusual. 

Anhydride  of  3-hydroxymercuri-4-methoxybenzoic  acid™ 

The  mercury  salt  of  anisic  acid  does  not  give  a  "basic"  salt  when 
boiled  with  water.    It  changes  only  on  heating  to  about  140°.    The 
mercury  probably  takes  the  position  meta  to  the  carboxyl  group. 
Sodium  salt  of  2-hydroxymercuri-4-methoxybenzoic  acid74 

68Blumenthal  and  Oppcnheim,  Biochem.  Z.  39  (1912),  51.  Chem.  Abst.  6  (1912), 
1467. 


™Schoeller,  Schrauth,  and  Miiller,  Biochem.  Z.  33  (1011),  309.     D.  R.  P.  216,267. 
D.  R.  P.  255,030.     Chem.  Zentr.  1913  I  353. 
T1D.  R.  P.  255,030,  Hid. 
72  Lajoux,  loc.  cit. 
&id  . 
.  R.  p.  234,054.     Frankel,  665. 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      321 

Mercury  compound  of  veratric  acid,  3,  4-dimethoxybenzoic  acid.75 

Mercury  compounds  of  tyrosine™ 

Mercury  derivatives  of  di-iodotyrosin.77 

Isatin  mercury  compounds78 

Mercury  derivatives  of  hydroxynaphthoic  acids™ 

Phthalic  acid  reacts  with  mercuric  acetate  on  refluxing  and  loses 
carbon  dioxide  forming  the  anhydride  of  o-hydroxymercuribenzoic 
acid.80 

Mercury  phthalimide.    N  —  Hg  compound.81 


Mercury  Derivatives  of  Phenolphthalein  and  Belated  Compounds.82 

A  great  variety  of  compounds  of  this  type  have  been  mercu- 
rated.  Among  these  are  phenolphthalein,  fluorescein,  methyl  fluores- 
cein,  dibromfluorescein,  tetrabromfluorescein,  tetraiodofluorescein,  te- 
traiodophenolphthalein,  quinolphthalein,  resorcin  succinein,  cresorcin 
succinein,  resorcin  saccharein.  In  several  cases  the  compounds  have 
been  carefully  studied  and  the  results  are  available  in  the  literature.83 

In  some  cases  mercuration  is  carried  out  by  heating  the  sodium  salt 
with  mercuric  oxide.  By  this  method  3  mercury  atoms  can  be  intro- 
duced into  phenolsulfonephthalein,  two  into  fluorescein,  and  one,  with 
difficulty,  into  phenolphthalein.  This  method  will  not  serve  to  intro- 
duce mercury  into  the  di-  or  tetra  halogen  fluoresceins.  If  mercuric 
acetate  is  used  in  alcohol  or  water  solution  or  suspension  all  of  the 
positions  ortho  to  phenolic  oxygen  are  replaced  by  mercury  except 
in  the  case  of  phenolphthalein  into  which  only  three  atoms  of  mer- 
cury can  be  introduced  instead  of  the  expected  four. 

«  D.  R.  P.  249,332.     Chem.  Zentr.  1912  II  465.     Frankel,  665. 

78  R.  Hofmann,  Ann.  87  (1853),  124.  D.  R.  P.  279,957.  Chem.  Zentr.  1914  II 
1334.  Buchtala,  Chem.  A1)8t.  12  (1918),  1909;  10  (1916),  805,  1578,  1693.  D.  R.  P. 
279,957.  Frankel,  661. 

"  D.  R.  P.  279,957,  loc.  cit. 

"Peters,  Ber.  40  (1907),  235. 

"Brieger  and  Schulemann,  J.  prakt.  Chem.   (2)   89   (1914),  176. 

80Pesci,  Qazz.  chim.  ital.  32  II   (1902),  279. 

81  Landsberg,  Ann.  215   (1882),  189. 

82  White,  J.  Am.  Chem.  Soc.  42   (1920),  2355.     D.  R.  P.  308,335.     Chem.  Abst.  13 
(1919),  1621. 

88  Zftttf. 


322  COMPOUNDS  OF  MERCURY 

Tri-acetoxymercuri  phenolphthalein84 

Phenolphthalein  and  mercuric  acetate  are  heated  in  dilute  alcohol 
and  acetic  acid.  Rosetted  needles.  (Hg,HOAc).  At  120°  it  loses 
one  molecule  of  acetic  -acid,  probably  forming  an  anhydride  of  an 
o-hydroxymercuri  phenol. 

Hydroxymercuri  phenolphthalein.85 

It  is  prepared  by  boiling  a  solution  of  phenolphthalein  in  dilute 
sodium  hydroxide  with  mercuric  oxide  for  three  hours.  The  alkaline 
solution  is  filtered  to  remove  a  black  residue  and  precipitated  by 
carbon  dioxide  as  a  purplish  white  amorphous  solid.  (Hg).  It  is  in- 
soluble in  common  solvents  except  acetic  acid. 

Di-acetoxymercuri-o-cresolphthalein.86 

The  preparation  in  water  solution  forms  considerable  amounts  of 
mercurous  acetate.  The  product  is  a  yellow  granular  substance  (Hg). 
It  is  insoluble  in  common  solvents  but  soluble  in  bases  giving  a 
purple  solution. 

Tri-hydroxymercuri  phenolsulfonephthalein87 

An  alkaline  solution  of  the  phthalein  is  boiled  with  mercuric  oxide 
for  several  hours.  The  purple  solution  is  cleared  by  means  of  the 
centrifuge  and  evaporated  on  a  steam  bath.  It  leaves  a  purple  powder 
with  a  bronze  luster.  (Hg). 

Tetra-acetoxymercuri  phenolsulfonephthalein88 

This  substance  could  not  be  obtained  pure  by  boiling  the  phthalein 
with  mercuric  acetate.  Instead  a  substance  is  obtained  which  gives 
analyses  indicating  that  it  is  a  mixture  of  one  molecule  of  this  sub- 
stance with  two  molecules  of  its  hydrolysis  product,  tetra-hydroxy- 
mercuri  phenolsulfonephthalein.  The  hydrolysis  cannot  be  made  com- 
plete. The  product  is  insoluble  in  all  solvents  except  methyl  alcohol, 
hot  acetic  acid,  and  sodium  hydroxide.  In  the  latter  it  gives  a  bluish 
purple  solution. 

»*  White,  loc.  cit.  2362. 
85/6id.  2360. 

86  Ibid. 

87  lUd 
*»Jl)id.  2365, 


MERCURY  DERIVATIVES  OF  AROMATIC  ACIDS      323 

Tetra-acetoxymercuri  fluorescein.99 

As  is  the  case  of  the  preceding  compound  this  substance  is  not 
obtained  pure  but  in  a  partly  hydrolyzed  condition.  The  product 
from  fluorescein,  sodium  hydroxide  and  mercuric  oxide  is  about  two- 
thirds  hydroxide  and  one-third  acetate.  It  is  insoluble  in  common  sol- 
vents but  soluble  in  bases.  An  alkaline  solution  of  iodine  gives  the 
color  of  erythryrosin. 

Hydroxymercuri  fluorescein90 

Prepared  from  an  alkaline  solution  of  fluorescein  and  one  molecule 
of  mercuric  oxide.  Treated  with  dilute  HC1  it  gives  a  chloromercuri 
compound.  (Cl) .  With  sulfuric  acid  it  gives  the  hydroxymercuri  com- 
pound. 

Di-hydroxymercuri  fluorescein. 

It  is  prepared  like  the  preceding  compound  but  by  the  use  of  two 
molecules  of  mercuric  oxide.  It  forms  iridescent  green  scales.  (Hg) . 

Hydroxymercuri-dibromo-  fluorescein.91 

Prepared  from  an  alkaline  solution  of  dibromofluorescein  boiled 
with  mercuric  acetate  and  acetic  acid  until  a  sample  gives  no  action 
with  ammonium  sulfide.  (Hg) .  Less  than  one  per  cent  of  acetic  acid 
is  obtained  from  the  substance  showing  that  the  change  to  the  hy- 
droxymercuri compound  is  almost  complete.  The  product  is  a  red  pow- 
der, insoluble  in  common  solvents,  soluble  in  two  molecules  of  sodium 
hydroxide  giving  a  deep  red  solution.  It  is  soluble  in  ammonium  sul- 
fide. Mercuric  sulfide  separates  slowly  from  this  solution. 

Mercury  vanillin  is  a  white  tasteless  solid,  soluble  in  water,  soluble 
in  dilute  acids.  It  is  a  sweet  smelling  powder  containing  401  per  cent 
of  mercury.92 

"White,  J.  Am.  Chem.  8oc.  42  (1920),  2363. 

M  Ibid.  2360. 

81  Ibid.  2363. 

92  Realenzylc.  Pharm.  VII  100. 


Chapter  XIII. 

Mercury  Derivatives  of  Aromatic  Ketones,  Terpenes,  and 
Related  Compounds. 

Derivatives  of  Acetophenone. 

Phenacyl  mercuric  chloride,  C6H5  —  CO  —  CH2  —  HgCl.1 

Mercuric  acetate  is  heated  with  an  excess  of  acetophenone  at  150° 
until  no  mercuric  ions  can  be  detected  by  sodium  hydroxide.  The  clear 
solution  is  filtered  from  the  mercury  which  is  formed,  into  a  sodium 
chloride  solution.  The  precipitate  is  washed  with  small  portions  of 
ether  to  remove  any  unchanged  acetophenone.  It  is  recrystallized 
from  high  boiling  ligroin  or  acetone.  M.P.  145-6°  (C,  high,  HHg). 
The  mercury  is  very  loosely  attached.  Warm  dilute  hydrochloric  acid 
gives  acetophenone.  Even  cold  dilute  ammonium  sulfide  gives  HgS 
at  once.  Bromine  dissolved  in  potassium  bromide  gives  phenacyl  bro- 
mide which  is  identified  by  its  melting  point,  analysis,  and  the  forma- 
tion of  the  aniline  compound  melting  at  94°.  The  mercuration  of 
acetophenone  gives  a  small  amount  of  dimercurated  product. 

Phenacyl  mercuric  chloride  reacts  with  ethyl  magnesium  bromide 
in  an  atmosphere  of  hydrogen  giving  the  tertiary  alcohol  (Chloro- 
mercuri  methyl) -ethyl-phenyl-carbinol.  M.P.  129-30°  decomp.  It  is 
a  yellow  solid  which  can  be  recrystallized  from  ether.  (CHHg).  It 
gives  mercuric  sulfide  at  once  with  ammonium  sulfide. 

Acetophenone  is  said  to  react  with  alkaline  mercuric  iodide.2  It  re- 
acts with  mercuric  oxide  if  heated  for  a  long  time  at  100°.  The  re- 
sulting product  is  a  pale  yellow  insoluble  compound  which  reacts  with 
hydrochloric  acid  giving  acetophenone.3 

It  reacts  with  alkaline  mercuric  cyanide  solution  giving  a  light 

1Dimroth,  Ber.  35  (1902),  2870.  Grignard  and  Abelmann,  Bull.  soc.  cMm.  (4)  19 
(1916),  19. 

2  Marsh  and  Fleming-Struthers,  J.  Chem.  Soc.  95  (1909),  1778. 
•Hantzsch  and  Auld,  Ber.  38   (1905),  2683. 

324 


DERIVATIVES— AROMATIC  KETONES,  TERPENES,  ETC.    325 

yellow  precipitate  which  gives  analyses  for  C,  H,  N,  Hg,  and  CN  which 
agree  very  well  with  the  formula,  C24H1803Hg4(CN)2.4 

Mercury  Derivatives  of  Benzophenone.5 

Alkaline  mercuric  iodide  or  mercuric  oxide  give  no  action  on 
benzophenone  which  thus  differs  from  ketones  which  are  capable  of 
forming  an  enol  modification.  Mercuric  acetate  reacts  with  benzo- 
phenone at  150°  giving  an  ortho  mercurated  product. 

o-Chloromercuri  benzophenone.6 

Dry  mercuric  acetate  is  heated  with  three  molecules  of  benzophe- 
none in  a  bulb  at  150°  until  the  reaction  is  complete.  The  warm  mix- 
ture is  poured  into  sodium  chloride  solution  and  then  cooled  and  shaken 
with  ether.  Evaporation  of  the  ether  leaves  benzophenone  and  the  mono 
compound  and  a  small  amount  of  a  dimercurated  product  of  unproved 
structure.  The  benzophenone  is  removed  by  hot  ligroin.  The  residue  is 
repeatedly  crystallized  from  alcohol.  Shining  leaflets.  M.P.  167-8°. 
It  is  easily  soluble  in  acetone,  chloroform,  and  ethyl  acetate,  very 
difficultly  soluble  in  ligroin.  Yield  40°  of  weight  of  mercuric  acetate 
used.  (CHHg).  Boiling  hydrochloric  acid  splits  the  C  —  Hg  linkage. 
Hydrogen  sulfide  acts  very  slowly  even  on  heating.  Ethyl  magnesium 
bromide  forms  a  mercurated  tertiary  alcohol. 

Phenyl  o-chloromercuriphenyl  ethyl  carbinol. 

Is  prepared  in  the  same  way  as  the  corresponding  compound  from 
phenacyl  mercuric  chloride.  It  is  recrystallized  from  a  mixture  of 
ether  and  ligroin.  M.P.  106°  decomp.  (CHHg) .  It  reacts  vigorously 
with  Grignard  reagents.  It  gives  no  action  in  the  cold  with  ammo- 
nium sulfide  or  hydrogen  sulfide. 

o-Bromomercuri  benzophenone. 

It  is  prepared  from  the  mercuration  mixture  and  sodium  bromide. 
It  is  less  soluble  in  ether  and  alcohol  than  the  chloride.  M.P.  176° 
(CHHgBr).  Treatment  with  bromine  yields  o-bromobenzophenone. 
This  substance  is  identified  by  its  melting  point,  its  oxime,  and  the 
phenyl  indoxazene  obtained  from  the  latter. 

*  Marsh  and  Fleming-Struthers,  J.  Chem.  Soc.  87   (1905),  1881. 

'Dimroth,  Ber.  35  (1902),  2868.  Auld  and  Hantzsch,  Ber.  38  (1905),  2677.  Marsh 
and  Fleming-Struthers,  J.  Chem.  Soc.  95  (1909),  1778.  Grignard  and  Abelmann,  Bull, 
soc.  chim.  (4)  19  (1916),  20. 

•  Dimroth,  loc.  cit.    Grignard  and  Abelmann,  loc.  cit.  24. 


326  COMPOUNDS  OF  MERCURY 

2-Chloromercuri  indandione.1 

The  sodium  derivative  of  indandione  is  treated  with  an  excess 
of  mercuric  chloride.  (ClHg).  The  product  is  a  yellow  solid  easily 
soluble  in  pyridine,  difficultly  soluble  in  sodium  hydroxide.  Cold 
sodium  carbonate  solution  changes  it  to  the  corresponding  hydroxide. 

2-Hydroxymercuri  indandione.8 

Is  prepared  from  the  chloride  by  shaking  two  days  with  sodium 
carbonate  solution.  The  residue  is  washed  with  dilute  acetic  acid  to 
remove  any  mercuric  oxide.  White  solid.  (Hg) . 

2-chloromercuri-2-acetyl-indandione? 

Is  prepared  from  the  sodium  salt  and  mercuric  chloride.  White 
microcrystalline  powder. 

2-Chloromercuri-2-carbethoxy-indandione. 

The  sodium  compound  and  mercuric  chloride  on  standing  several 
days  give  colorless  cubes.  M.P.  240-5°  (ClHg).  Insoluble  in  com- 
mon solvents,  soluble  in' pyridine  with  yellow  color.  When  the  pyri- 
dine solution  is  treated  with  water  a  precipitate  of  HgCl2.2C5H5N  is 
formed.  The  other  product  is  not  mentioned. 

2,  2'-Mercuribis-2-carbethoxy  indandione™ 

It  is  prepared  from  the  sodium  compound  and  mercuric  acetate. 
(Hg). 

Mercury  Compounds  Formed  from  Terpineol.10a 

OH 


OH  /\°H 

Terpineol.  Terpinol.  Cineol. 

(Terpine). 

Terpineol  does  not  give  any  satisfactory  product  with  acid  solu- 
tions of  mercuric  salts.    Mercuric  oxide  is  dissolved  in  20  per  cent  nit- 

7  Peters,  Ber.  40  (1907),  239. 

8  Ibid. 

•Hantzsch  and  Gajewski,  Ann.  392   (1912),  309. 

10  Ibid.  307. 

loa  Sand  and  Singer,  Ber.  35   (1902),  3171. 


DERIVATIVES— AROMATIC  KETONES,  TERPENES,  ETC.    327 

ric  acid  and  the  solution  is  treated  with  10  per  cent  potassium  hy- 
droxide until  the  white  basic  salt  begins  to  form.  A  solution  of  ter- 
pineol  in  ether  is  added  and  shaken  until  the  precipitate  dissolves. 
Potassium  hydroxide  is  added  until  the  basic  salt  is  again  precipitated. 
This  is  dissolved  by  the  addition  of  more  terpineol  solution.  These 
processes  are  kept  up  until  addition  of  potassium  hydroxide  gives  a 
black  precipitate.  The  water  layer  is  then  separated  and  filtered.  The 
amount  of  mercury  in  the  solution  is  carefully  determined  by  analyzing 
an  aliquot  part.  The  solution  is  made  strongly  alkaline  with  con- 
centrated potassium  hydroxide  and  the  calculated  amount  of  potas- 
sium iodide  solution  is  added  in  three  portions.  The  alkali '  insolu- 
ble cineol  mercuric  iodide  precipitates  at  once.  In  a  few  days  the 
filtrate  gives  crystalline  crusts  of  the  high  melting  a-trans-terpinol 
mercuric  iodide.  The  filtrate  from  this  substance  when  treated  with 
carbon  dioxide  gives  a  precipitate  of  the  low  melting  (3  form  of  trans- 
terpinol  mercuric  iodide,  the  chief  product  of  the  reaction.  Another 
product,  yellow  and  amorphous  is  obtained. 

Hgl 

L   L         I 


OH     Hgl  OH 

a-Trans-terpinol  mercuric  iodide.     (3-Trans-terpinol  mercuric  iodide. 

Stable  form.  Labile  form. 

High  melting.  Low  melting. 

If  the  solution  is  strongly  enough  alkaline  before  the  addition  of 
potassium  iodide  the  mercury  cineol  iodide  contains  some  of  the  p-ter- 
pinol  iodide.  This  can  be  extracted  with  cold  alcohol.  This  alcoholic 
extract  when  treated  with  water  and  evaporated  under  diminished 
pressure  gives  some  of  the  a  iodide,  then  a  mixture  of  the  a  and  (3  and 
finally  an  oil  which  is  mainly  the  p  form. 

%-Chloromercuri  cineol.1* 

Is  prepared  by  adding  the  calculated  amount  of  potassium  chloride 
to  the  solution  obtained  from  terpineol  and  basic  mercuric  nitrate 
without  the  addition  of  a  large  excess  of  alkali.  After  the  mixture 
has  been  allowed  to  stand  for  24  hours  it  is  treated  with  carbon  di- 
oxide. The  precipitate  is  recrystallized  from  alcohol.  It  forms  white 

»  76id.  3175. 


328  COMPOUNDS  OF  MERCURY 

matted  needles.  M.P.  162°.  It  is  soluble  in  alkalies  thus  differing 
from  the  iodide.  Otherwise  its  solubilities  are  like  those  of  that  sub- 
stance. (CHHg).  When  reduced  with  sodium  amalgam  it  gives  an 
oil  which  may  be  impure  cineol.  Treatment  with  sodium  stannite 
gives  mercury  dicineolyl. 

2-Iodomercwri  cineol.12 

Is  prepared  as  outlined  above.  86  gm.  of  mercuric  oxide  gives  16 
gm.  of  the  iodide.  It  crystallizes  from  alcohol  in  beautiful  small 
prisms.  Turns  yellow,  115°,  melts  152-4°  decomp.  (CHIHg).  It  is  in- 
soluble in  alkalies  and  potassium  iodide  solution.  It  dissolves  in  con- 
centrated mineral  acids  with  decomposition.  It  is  difficultly  soluble  in 
ether  and  cold  alcohol,  easily  in  hot  alcohol,  very  soluble  in  cold 
benzene  and  chloroform.  Reduction  with  sodium  amalgam  gives  an 
oil  which  does  not  crystallize  on  long  standing  or  when  seeded  with 
terpineol  crystals.  It  may  be  impure  cineol.  The  iodide  gives  no  ben- 
zoate  when  treated  with  benzoyl  chloride  and  pyridine  showing  it  is 
not  a  derivative  of  terpineol. 

2,  2'-Mercuribis-cineol,  2-Mercury  dicineolyl™ 

Is  prepared  from  the  chloride  and  sodium  stannite.  It  is  an  oil 
insoluble  in  alkalies,  but  easily  decomposed  by  acids  giving  terpineol. 
It  gives  a  compound  containing  oxalic  acid  when  treated  with  an  ether 
solution  of  that  substance.14 

a-Form  of  2-iodomercuri-trans-terpineol.  (Stable,  high  melting  form.) 
Preparation  as  above.  It  crystallizes  from  benzene  in  small  color- 
less crystals  which  are  sensitive  to  light.  It  turns  red  at  120°,  melts 
144°  decomp.  (CHIHg) .  Soluble  in  strong  potassium  hydroxide,  diffi- 
cultly soluble  in  cold  benzene  and  ethyl  acetate,  easily  soluble  in  alco- 
hol, ether,  and  hot  benzene.  It  can  be  obtained  by  evaporating  an  ether 
solution  of  the  labile  (3-isomer.  It  forms  a  fairly  stable  compound 
with  one  molecule  of  alcohol.  This -is  easily  soluble  in  cold  absolute 
alcohol.  It  separates  in  shining  needles.  M.P.  123-5°  turning  red 
(CHHg,C2H5OH) .  Solution  in  benzene  gives  the  a-iodide.  M.P.  144°. 
Electrolytic  reduction  of  an  alkaline  solution  of  the  iodide  gives  pure 
trans- terpinol.  M.P.  156°.  Reduction  by  sodium  amalgam  gives  an 
85  per  cent  yield  of  the  same  substance. 

» Ibid.  3174. 
» Ibid.  3176. 
"/bid.  3177. 


DERIVATIVES— AROMATIC  KETONES,  TERPENES,  ETC.    329 

fi-Form  of  2-iodomercuri-trans-terpinol.  (Labile,  low  melting  form.) 
Is  prepared  by  passing  carbon  dioxide  into  the  cooled  liquid  from 
which  cineol  mercuric  iodide  and  the  a-terpinol  mercuric  iodide  have 
separated.  The  white  precipitate  is  purified  by  dissolving  in  potassium 
hydroxide  and  precipitating  fractionally  by  carbon  dioxide.  M.P.  38°. 
It  separates  from  benzene  solution  as  a  clear  oil.  (CH) .  It  is  very  solu- 
ble in  alcohol,  ether,  ethyl  acetate,  rather  difficultly  in  cold  benzene, 
and  ligroin,  easily  soluble  in  potassium  hydroxide  or  potassium  iodide 
solution.  Reduction  by  sodium  amalgam  gives  trans-terpinol.  It  is 
easily  soluble  in  cold  acetic  acid.  When  this  solution  is  heated  it 
suddenly  gives  a  mass  of  white  crystals  of  the  a-iodide  melting  at  144°. 
About  two-thirds  of  the  beta  form  is  changed.  On  standing  in  cold 
alcohol  solution  the  beta  iodide  slowly  gives  crystals  of  the  alcohol 
compound  of  the  alpha  iodide,  M.P.  123°.  Recrystallization  of  the 
beta  form  from  benzene  gives  a  mixture  of  the  two  isomers.  The 
change  from  the  beta  form  to  the  more  stable  form  takes  place  very 
slowly  in  alkaline  solution.15  Dimethyl  heptenol  has  a  structure  much 
like  that  of  terpineol. 

CH3  CH3 

i  A 

/    \  /\ 

CH2    CH  CH3    CH 

CH2    CH2  CH2 

\/  / 

CH  CH2 

C  — OH  C  — OH 

/\  /\ 

CH3    CH3  CH3    CH3 

Terpineol.        Dimethyl  heptenol. 

When  treated  with  mercuric  acetate  it  gives  a  mercurated  inner 
ether  analogous  to  mercury  cineol  iodide  and  a  mercurated  glycol 
much  like  the  mercurated  trans-terpinol.  This  glycol  appears  to  ha"ve 
an  oily  modification  analogous  to  the  beta  form  of  the  terpinol  com- 
pound. 

18  Ibid.  3184. 


330  COMPOUNDS  OF  MERCURY 

S-Iodomercuri-2,  6-dimethyl-2,  6-epoxyhexane. 

Is  formed  from  dimethyl  heptenol  and  mercuric  acetate  treated 
with  potassium  hydroxide  after  a  few  seconds.  It  is  an  oil,  insoluble  in 
concentrated  KOH,  soluble  in  absolute  alcohol  and  ether.  (CH) . 

S-Iodomercuri-2,  6-dimethyl-hexandiol,  2,  6. 

Is  prepared  by  passing  carbon  dioxide  into  the  alkaline  filtrate 
from  the  preparation  of  the  preceding  compound.  The  precipitate  is 
extracted  with  ether.  This  on  evaporation  leaves  an  oil  which  solidi- 
fies on  standing  or  if  warmed  with  benzene.  It  crystallizes  from 
benzene.  M.P.  124-5°  sharp.  It  is  sensitive  to  light.  (CH).  It  dis- 
solves in  potassium  hydroxide. 

Mercury  Derivatives  of  Camphor.16 

Camphor  reacts  with  an  alkali  and  mercuric  iodide  giving  complex 
mercury  compounds  which  are  formulated  as,  (C10H140)Hg2I2, 
(C10H140)3Hg4I2,  (C10H140)4Hg5I2,  and  (C10H140)5Hg6I2.  Treatment 
of  these  compounds  with  iodine,  iodine  chloride,  or  iodine  bromide 
gives  di-iodocamphor  which  can  be  changed  to  camphoquinone.  This 
indicates  that  the  alpha  hydrogen  atoms  of  camphor  are  replaced  by 
mercury. 

oja-Di-iodomercuri  camphor.17 

Is  prepared  from  camphor  and  a  cold  potassium  hydroxide  solution 
and  mercuric  iodide.  It  can  also  be  prepared  by  adding  cold  acetic 
acid  to  the  yellow  precipitate  of  (C10H140)3HgJ2  formed  from  camphor 
boiled  with  an  alkaline  solution  of  potassium  mercuric  iodide.18 

It  forms  a  colorless  amorphous  powder,  insoluble  in  water  and 
neutral  solvents.  It  sublimes  without  decomposition.  It  is  not  changed 
by  aqueous  potassium  iodide.  It  is  insoluble  in  alcohol  and  acetone. 
A  mixture  with  potassium  iodide  is  soluble  in  alcohol  and  acetone. 

a-Acetoxymercuri  camphor. 1Q 

Is  prepared  by  dissolving  (C10H140)3Hg4I2  in  hot  acetic  acid. 

18  Marsh  and  Fleming- Struthers,  J,  Chem.  Soc.  95  (1909),  1778.  Marsh,  J.  Chem. 
Soc.  97  (1910),  2413. 

"Marsh  and  Fleming-Struthers,  J.  Chem.  Soc.  95   (1909),  1783. 

18  Ibid.  1780. 

19  Ibid.  1782. 


DERIVATIVES—  AROMATIC  KETONES,  TERPENES,  ETC.    331 

a-Halidemercuri  camphor. 

If  (C10H140)3HgJ2  is  treated  with  cold  acetic  acid  and  then  with  a 
chloride  or  bromide  solution  the  corresponding  halide  is  obtained. 
The  chloride  is  slightly  soluble  in  dilute  acetic  acid,  giving  good  crys- 
tals. It  melts  222°  (ClHg). 

The  bromide  is  insoluble  in  water,  soluble  in  acetic  acid  giving 
colorless  crystals  which  melt  at  220-1°  (BrHg)  .  The  iodide  is  obtained 
in  this  way  in  the  form  of  a  double  salt  with  a  molecule  of  mercuric 
iodide.  If  an  excess  of  potassium  iodide  is  added  in  the  presence  of 
acetic  acid  the  C  —  Hg  compound  is  decomposed.  If  the  treatment 
with  an  excess  of  potassium  iodide  is  carried  out  in  a  neutral  medium 
the  molecule  of  mercuric  iodide  is  removed  leaving  the  iodomercuri 
camphor.  (CHIHg)  . 

Oxide  of  a-mercuri  camphor.20 

The  acetate  solution  obtained  from  (C10H140)3Hg4I2  is  treated  with 
an  excess  of  10  per  cent  chloride-free  sodium  hydroxide.  The  pre- 
cipitate is  readily  soluble  in  alcohol  and  carbon  disulfide.  No  good 
crystals  are  obtained.  Heated  above  100°  it  apparently  gives  a  more 
complicated  mercurated  camphor.  (CHHg).  Treated  with  acids  it 
gives  various  salts  such  as  the  sulfate,  nitrate,  oxalate,  and  benzoate. 

Camphocarboxylic  acid  and  its  esters  give  stable  organic  mercury  com- 
pounds.21 

Mercury  Derivatives  of  Camphene.22 

Camphene  dissolved  in  petroleum  ether  is  shaken  with  a  saturated 
solution  of  two  molecules  of  mercuric  acetate  for  thirty  days.  A  white 
resinous  substance  is  formed  which  gradually  hardens.  Yield  90  per 
cent.  Slightly  soluble  in  water  and  alcohol.  M.P.  188-9°.  Analyses 
for  C,  H,  and  Hg  agree  with  the  formula  (C10H160)  (HgOAc)2.  This 
formula  would  indicate  that  one  molecule  of  basic  mercuric  acetate 
has  added  to  the  molecule  and  that  one  acetoxymercuri  group  has 
been  introduced  in  place  of  a  hydrogen  atom.  It  reacts  slowly  with 
dilute  hydrochloric  acid  and  hydrogen  sulfide  forming  camphene.  The 


.  1785. 

21  D.  R.  P.  275,932.     Chem.  Zentr.  1914  II  367.     Frankel,  667. 

"Balbiano  and  Paolini,  Atti  accad.  Lined  (5)  11  I  (1902),  65.     Chem.  Zentr.  1902 
II  844.     Ber.  36  (1903),  3576.     Qazz.  chim.  ital.  36  I  (1906),  250. 


332  COMPOUNDS  OF  MERCURY 

corresponding  dichloromercuri  compound  is  prepared  from  the  acetate 
and  sodium  chloride.  It  is  an  amorphous  white  powder,  insoluble  in 
all  neutral  solvents.  It  softens  at  150°  but  does  not  melt  at  250° 
(ClHg).  Treatment  with  sodium  amalgam  or  with  zinc  and  sodium 
hydroxide  gives  an  odor  of  camphene.  Heating  gives  some  camphene. 
Treatment  of  pinene 2S  with  mercuric  acetate  gives  mercurous 
acetate  and  an  oxidation  product,  A6(6)-hydroxy-menthen-2-one. 

Mercury  Compounds  of  Resins  and  Gluco sides.24 

23  IUd.}  see  also  Balbiano  and  Paolini,  Ber.  35  (1902),  2995. 

2*Schoeller  and  Schrauth,  Chem.  Atst.  10   (1916),  395.     Leys,  J.  pharm.  chim.   (6) 
21   (1905),  388.     Chem.  Zentr.  1905  I  1532.     Schmidt,  Pharmazeutische  Chem.  II  2002. 


Chapter  XIV. 

Mercury  Derivatives  of  Heterocyclic  Compounds,  Azo 
Compounds,  and  Aromatic  Arsenicals. 

Mercury  Compounds  of  Thiophene. 

Thiophene  reacts  with  an  acid  solution  of  mercuric  sulfate  giving 
a  series  of  compounds  which  are  formulated  as  double  salts  with  mer- 
curic sulfate  and  mercuric  oxide.1 

a-Chloromercuri  thiophene.2 

Thiophene  in  alcohol  is  treated  with  saturated  mercuric  chloride 
solution  and  a  33%  solution  of  sodium  acetate.  After  several  days 
a  white  crystalline  precipitate  is  formed.  Yield  25  gm.  from  10  gm. 
of  thiophene.  The  mono-mercury  compound  is  separated  from  the  di- 
mercury  compound  by  extraction  with  hot  alcohol.  It  is  almost  in- 
soluble in  cold  water,  slightly  soluble  in  hot.  It  is  recrystallized  from 
hot  acetone  or  chloroform.  M.P.  183°.  If  heated  for  some  time  it 
becomes  solid  and  does  not  melt  again.  It  is  slightly  volatile  and 
sublimes  even  at  100°  and  very  rapidly  at  210°.  If  heated  in  large 
amounts  it  is  blackened.  (CHClSHg).  The  chloride  is  soluble  in  a 
large  volume  of  4%  sodium  hydroxide.  It  is  precipitated  unchanged 
by  acetic  acid. 

Reactions. 

1.  With  halogens.3 

It  does  not  react  with  iodine.     This  is  the  more  peculiar  as  the 

2,  5-dichloromercuri  thiophene  does  react  with  halogens. 
2.    With  acid  halides. 

Treatment  with  aliphatic  and  aromatic  acid  chlorides  gives  thien- 
ones.  The  reaction  is  modified  so  that  thiophene  and  the  acid  chloride 
are  treated  with  a  small  amount  of  the  chloromercuri  compound  which 

1Denig6s,  Bull.  soc.  chim.  (3)  13  (1895),  538;  (3)  15  (1896),  1064.  Ann.  chim. 
phys.  (7)  18  (1899),  1420;  (8)  12  (1907),  398. 

'Volhard,  Ann.  267  (1892),  176,  180.  Steinkopf  and  Bauermeister,  Ann.  403 
(1914),  55.  Finzi,  Gazz.  chim.  ital.  45  II  (1915),  283.  Chcm.  Zentr.  1916  I  474. 
Steinkopf,  Ann.  413  (1917),  318.  Chem.  Abst.  11  (1917),  2326. 

»  Volhard,  loc.  cit.  180. 

333 


334  COMPOUNDS  OF  MERCURY 

acts  as  a  catalyst.  In  this  way  the  acid  halides  of  the  following  acids 
have  been  employed:  acetic,  benzoic,  o-toluic,  p-toluic  and  p-nitroben- 
zoic.  This  reaction  of  acid  chlorides  with  the  C  —  Hg  linkage  to 
form  a  new  C  —  C  linkage  is  one  which  would  be  expected  and  which 
should  prove  useful  in  synthetic  work.  Unfortunately  it  appears  to 
be  confined  to  the  thiophene  series. 

3.  With  arsenic  chloride. 

The  reaction  takes  place  readily  on  heating  giving  R  —  AsCl2  and 
a  small  trace  of  R2AsCl.  The  same  product  can  be  obtained  by  heat- 
ing thiophene  with  arsenic  trichloride  using  a  trace  of  mercuric  chlo- 
ride as  a  catalyst. 

4.  With  metallic  sodium. 

The  chloride  when  heated  in  xylene  solution  with  sodium  gives  the 
R2Hg  compound,  a-mercury  dithienyl.  Yield  50%.  This  reaction  is 
a  good  illustration  of  the  ease  of  changing  from  R  —  Hg  —  X  to  R2Hg 
in  the  thiophene  series.  Most  C  —  Hg  compounds  react  with  metallic 
sodium  giving  metallic  mercury. 

5.  With  inorganic  iodides. 

An  acetone  solution  of  the  chloride  reacts  with  one  molecule  of 
a  similar  solution  of  sodium  iodide  to  give  a  mixture  of  the  corre- 
sponding iodide  and  mercury  dithienyl.  This  is  unusual  as  a  large 
excess  of  iodide  is  ordinarily  required  to  give  the  R2Hg  compound. 
If  an  excess  of  sodium  iodide  is  used  the  yield  of  mercury  dithienyl  is 
almost  quantitative.  Apparently  the  tendency  to  form  R2Hg  is  so 
great  in  the  thiophene  series  that  the  corresponding  iodide  as  soon  as 
formed  tends  to  change  to  mercuric  iodide  and  R2Hg  without  any  excess 
of  sodium  iodide  to  form  a  complex  with  the  former  substance. 

a-Bromomercuri  thiophene. 

Is  prepared  by  boiling  mercury  dithienyl  and  mercuric  bromide  in 
acetone  solution.  It  is  easily  soluble  in  acetone,  fairly  soluble  on 
heating  in  alcohol,  chloroform,  carbon  disulfide,  benzene  and  toluene. 
It  is  recrystallized  from  toluene  in  silvery  leaflets.  M.P.  169-70°, 
after  sintering.  (SHg) . 

a-Iodomercuri  thiophene. 

Is  prepared  from  the  chloride  and  one  molecule  of  sodium  iodide 
in  acetone.  The  precipitate  consists  of  sodium  chloride  and  mercury 
dithienyl.  When  the  filtrate  is  treated  with  water  a  white  precipitate 


DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS      335 

is  formed.  Later,  some  mercuric  iodide  separates.  The  silvery  leaf- 
lets obtained  by  recrystallizing  from  alcohol  are  slightly  red  and  be- 
come more  so  on  rubbing  when  dry.  The  pure  iodide  can  be  obtained 
by  dissolving  mercury  dithienyl  and  mercuric  iodide  in  acetone  and  di- 
luting with  water.  It  then  forms  pure  white  crystals  which  are  not 
changed  by  rubbing.  Yield  90%.  M.P.  117°  (Hg).  In  concentrated 
solution  an  impure  product  is  obtained.  It  is  insoluble  in  water, 
slightly  soluble  in  hot  alcohol,  little  soluble  in  cold  benzene,  easily  hot, 
fairly  soluble  in  ether,  soluble  in  cold  acetone.  The  iodide  tends  to 
change  to  mercuric  iodide  and  mercury  dithienyl.  It  reacts  even  in 
the  cold  with  arsenic  triodide  giving  mercuric  iodide. 

a-Mercury  dithienyl. 

The  best  preparation  is  from  an  acetone  solution  of  the  chloride 
and  an  excess  of  sodium  iodide.  The  white  precipitate  is  washed  with 
water  to  remove  sodium  chloride  and  the  residue  is  dried  and  crystal- 
lized from  benzene.  M.P.  197°.  Insoluble  in  water,  hardly  soluble 
in  cold  alcohol,  not  easily  even  hot,  rather  difficultly  soluble  in  cold 
benzene  and  chloroform,  easily  hot,  fairly  soluble  even  in  cold  acetone. 
(Hg). 

Mercury  dithienyl  reacts  with  the  three  mercuric  halides  in  acetone 
solution  giving  thienyl  mercuric  halides  in  about  90%  yields.  In  each 
case  the  acetone  solution  is  diluted  with  water  to  precipitate  the 
product.  Mercury  dithienyl  reacts  with  arsenic  trichloride  spontane- 
ously, forming  mercuric  chloride  and  the  three  possible  substituted  ar- 
sines.  Primary  and  secondary  alkyl  halides  do  not  react  with  mercury 
dithienyl. 

However,  tertiary  butyl  iodide  reacts  vigorously  on  gentle  warming 
giving  an  oily  peculiar  smelling  liquid  which  has  not  been  purified. 

Di-mercurated  thiophenes* 
2-Acetoxymercuri-5-hydroxymercuri  thiophene. 

Is  prepared  by  refluxing  commercial  benzene  with  mercuric  ace- 
tate. After  half  an  hour  all  of  the  thiophene  has  been  removed  form- 
ing a  white  precipitate.  Thiophene  reacts  more  easily  than  benzene. 
Thus,  in  a  run  which  gave  32  gm.  of  the  thiophene  compound  only  .2 
gm.  of  phenyl  mercuric  acetate  was  formed.  It  decomposes  at  270° 

*Volhard,  loc.  cit.  177.  Dimrotb,  Ber.  32  (1899),  759.  Chem.  Zentr.  1899  I  936. 
Scbwalbe,  Ber.  38  (1905),  2208,  Steinkopf  and  Bauermeister,  Ann.  403  (1914),  62. 


336  COMPOUNDS  OF  MERCURY 

without'  melting.  It  is  soluble  only  in  acetic  acid  from  which  it  crystal- 
lizes slowly  in  very  fine  needles  of  the  diacetate  which  loses  acetic  acid 
very  easily.  (CHHg) .  There  seems  to  be  some  doubt  about  the  na- 
ture of  the  original  precipitate  as  it  is  found  to  contain  only  half  the 
theoretical  amount  of  sulfur.5 

2,  5-Dichloromercuri  thiophene. 

Is  prepared  in  the  usual  way  from  the  acetate.  It  forms  a  white 
earthy  powder  which  is  insoluble  in  common  solvents.  It  is  not 
acted  upon  readily  by  acids,  even  by  concentrated  nitric  acid.  It  gives 
no  action  with  alkalies.  (CHClSHg).  It  sinters  at  265°  and  decompo- 
ses at  about  275°.  The  dichloride  reacts  readily  with  iodine  and  water 
on  warming  forming  di-iodothiophene.  M.P.  40°  (I).  The  reaction 
with  bromine  is  not  so  smooth  as  an  oily  mixture  of  di-,  tri-,  and  tetra- 
bromothiophenes  is  formed. 

Mercury  Compounds  of  <x-Monosubstituted  Thiophenes.6 

5 -C  hloromercuri-2-methy i-  thiophene. 

Is  prepared  from  2-thiotolene  and  mercuric  chloride  and  sodium 
acetate.  Most  of  the  product  separates  in  13  hours.  Yield  44%.  It 
crystallizes  from  alcohol  in  shining  crystals.  M.P.  204°,  after  sinter- 
ing. (CHClSHg).  Warming  the  chloride  with  benzoyl  chloride  gives 
the  corresponding  phenyl  ketone. 

5-Chloromercuri-2-carboxyl-thiophene. 

Is  prepared  in  the  usual  way,  from  thiophene-2-carboxylic  acid. 
On  standing  about  ten  days  a  yellow  precipitate  forms.  Only  part  of 
this  is  soluble  in  ammonium  hydroxide.  If  the  residue  is  treated  with 
sodium  hydroxide  it  dissolves  giving  a  solution  from  which  dilute  hy- 
drochloric acid  precipitates  the  chloride  in  a  form  soluble  in  ammo- 
nium hydroxide.  It  is  practically  insoluble  in  water  and  common 
solvents.  The  soluble  and  insoluble  forms  give  the  same  analyses  for 
mercury  and  sulfur.  No  explanation  is  known  for  the  existence  of  these 
two  forms. 

5 -Chloromercuri-2-pheny  I- thiophene. 

Is  prepared  in  the  usual  way.  After  seven  days  the  product  is 
filtered  off.  The  shining  leaflets  are  recrystallized  from  a  large  volume 

8  Schwalbe,  loc.  cit. 

8  Steinkopf  and  Bauermeister,  loc.  cit.  63.  Volhard,  loc.  cit.  180,  Steinkopf,  loc. 
cit.  319. 


I 

DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS      337 

of  hot  alcohol.   M.P.  234°,  not  sharp.    (Hg).   It  is  very  little  soluble 
in  cold  alcohol  and  benzene  and  only  difficultly  soluble  hot. 

5-Halidemercuri-2-chlorothiophene. 

The  chloride  may  be  prepared  in  the  usual  way  from  the  substi- 
tuted thiophene  and  mercuric  chloride  and  sodium  acetate.  It  is  readily 
soluble  in  hot  alcohol.  Silvery  leaflets.  M.P.  213-9°,  after  sintering 
(SHg).  It  is  insoluble  in  water  and  ligroin,  difficultly  soluble  in 
cold  alcohol,  benzene,  toluene,  fairly  soluble  hot,  soluble  even  in  cold 
acetone.  The  bromide  is  prepared  from  the  R2Hg  compound  and 
mercuric  bromide  dissolved  in  hot  acetone  and  cooled  to  give  crystals. 
It  is  less  soluble  than  the  R2Hg  compound.  Yield  93%.  M.P.  191°. 
It  is  recrystallized  from  toluene,  in  felted  white  crystals.  (SHg) .  The 
iodide  may  be  prepared  from  the  chloride  by  treatment  with  one  mole- 
cule of  sodium  iodide.  In  this  case  none  of  the  R2Hg  compound  is 
formed. 

5,  5'-Mercuribis-2-chlorothiophene. 

Is  prepared  from  the  chloride  in  acetone  with  a  little  over  two 
molecules  of  sodium  iodide.  The  reaction  takes  place  in  the  cold.  The 
product  forms  silvery  crystals  from  alcohol.  M.P.  155°,  after  sin- 
tering. (SHg) .  It  is  fairly  soluble  in  acetone  and  ethyl  acetate,  diffi- 
cultly soluble  in  cold  benzene  and  chloroform,  easily  on  heating,  very 
difficultly  soluble  in  cold  alcohol,  fairly  in  hot,  very  little  soluble  in 
ligroin  even  on  heating. 

5-Halidemercuri-2-bromothiophene. 

The  chloride  is  prepared  in  the  usual  way.  It  forms  small  white 
needles  from  alcohol.  M.P.  225°,  after  sintering.  (SHg).  It  is  in- 
soluble in  water,  little  soluble  in  ether,  very  difficultly  in  cold  alcohol, 
fairly  well  in  hot,  little  soluble  in  cold  benzene  and  toluene,  fairly  on 
heating,  fairly  soluble  in  cold  acetone.  The  bromide  is  prepared  from 
the  R2Hg  compound  and  mercuric  bromide  in  acetone.  White  felted 
needles  separate  from  a  benzene  solution.  M.P.  197°,  after  sintering. 
(SHg) .  It  is  fairly  soluble  in  acetone  and  ethyl  acetate,  difficultly  in 
cold  benzene,  more  soluble  on  heating,  very  difficultly  soluble  in  cold 
alcohol,  little  soluble  even  on  heating.  The  iodide  is  made  from  the 
chloride  and  one  molecule  of  sodium  iodide.  In  this  case  none  of  the 
R2Hg  componnd  is  added  unless  an  excess  of  sodium  iodide  is  used. 
It  is  easily  soluble  in  carbon  disulfide,  acetone,  and  ethyl  acetate, 


338  COMPOUNDS  OF  MERCURY 

fairly  soluble  in  benzene  and  toluene,  little  in  cold  alcohol  and  chloro- 
form but  easily  on  heating.  It  crystallizes  from  alcohol  in  small  white 
crystals.  It  turns  slightly  red  in  light,  M.P.  119°  (SHg). 

5,  5'-Mercuribis-2-bromothiophene. 

It  is  prepared  from  the  chloride  and  two  molecules  of  sodium  chlo- 
ride in  the  least  possible  amount  of  acetone.  It  forms  white  felted 
crystals  from  benzene.  M.P.  183°,  after  sintering.  (SHg).  It  is  diffi- 
cultly soluble  in  cold  benzene  and  chloroform,  easily  on  heating,  diffi- 
cultly soluble  in  cold  alcohol  and  little  even  when  hot. 

•5-Halidemercuri-2-iodothiophenes. 

The  chloride  is  prepared  in  the  usual  way.  The  reaction  takes  three 
weeks.  The  product  crystallizes  from  alcohol  in  fine  felted  crystals. 
It  sinters  at  215°  and  melts  at  225°  (SHg).  It  is  insoluble  in  water 
and  ligroin,  very  difficultly  soluble  in  cold,  and  not  readily  even  in  hot 
alcohol  and  chloroform,  little  soluble  in  cold  benzene  and  acetone, 
fairly  soluble  hot.  Treated  with  acetyl  chloride  at  about  90°  it  gives  a 
poor  yield  of  the  corresponding  methyl  ketone.  Treatment  with  iodine 
and  water  gives  2,  5-diiodothiophene.  Treated  with  one  molecule  of 
sodium  iodide  it  gives  a  mixture  of  the  iodide  and  the  R2Hg  com- 
pound. In  this  it  apparently  differs  from  the  corresponding  2-chloro- 
and  2-bromothiophene  derivatives.  The  bromide  is  made  in  the  usual 
way  from  the  R2Hg  compound  and  mercuric  bromide.  It  is  recrystal- 
lized  rapidly  from  xylene  (long  boiling  gives  a  violet  color).  The 
white  felted  needles  darken  at  170°  (SHg) .  It  is  fairly  soluble  in  ace- 
tone, difficultly  in  carbon  disulfide  and  xylene,  very  difficultly  in  alco- 
hol and  benzene.  The  iodide  is  made  from  the  R2Hg  compound  and 
mercuric  iodide  in  acetone.  It  is  recrystallized  from  benzene  and  pe- 
troleum ether.  It  is  a  slightly  yellow  macrocrystalline  powder.  M.P. 
141-2°,  giving  a  cloudy  liquid  which  clears  at  165°.  It  turns  red  on 
rubbing  (possibly  impure).  (SHg).  It  is  fairly  soluble  in  acetone,  diffi- 
cultly in  cold  chloroform,  benzene,  xylene,  but  fairly  soluble  hot. 

5,  5'-Mercuribis-2-iodothiopliene. 

The  chloride  is  treated  with  more  than  two  molecules  of  sodium 
iodide  in  acetone.  It  sinters  at  200°,  melts  at  223-4°.  It  probably 
contains  some  of  the  corresponding  iodide.  It  crystallizes  from  hot 
xylene  in  light  yellow  needles.  M.P.  231°,  after  sintering.  (SHg). 


DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS     339 

It  is  very  difficultly  soluble  in  common  solvents,  only  dissolving  in 
hot  xylene. 

Mercury  Derivatives  of  2,  5-Disubstituted  Thiophenes.7 

2,  5-Dimethyl  thiophene  reacts  with  mercuric  chloride  and  sodium 
acetate  in  a  different  way  from  the  thiophenes  which  have  an  alpha 
position  unsubstituted.  In  this  case  a  compound  is  formed  which 
apparently  results  from  the  addition  of  a  molecule  of  basic  mercuric 
chloride  to  the  double  bond  and  the  union  of  this  molecule  with  a 
molecule  of  mercuric  chloride.  The  evidence  for  this  formulation  is 
based  on  a  mercury  analysis  and  the  fact  that  long  boiling  with  alcohol 
gives  3-chloromercuri-2,  5-dimethyl  thiophene.  The  formation  of  this 
intermediate  compound  suggests  the  possibility  that  all  mercurations 
of  aromatic  compounds  are  preceded  by  similar  additions  to  the  dou- 
ble bonds  of  the  nucleus.  The  2,  5-dihalogen  thiophenes  give  no  re- 
action with  mercuric  chloride  and  sodium  acetate  even  on  very  long 
standing  in  the  cold.  Heating  causes  the  separation  of  calomel. 

Compound  of  2,  5-dimethyl-2-hydroxy-3-chloromercuri-2,  3-dihydro- 

thiophene  and  HgCl2. 

Is  prepared  from  2,  5-dimethyl  thiophene,  mercuric  chloride  and 
sodium  acetate.  White  crystals  separate.  After  seven  days  the  crys- 
tals are  filtered  and  quickly  recrystallized  from  hot  alcohol.  M.P. 
186-7°  after  sintering.  (Hg).  Insoluble  in  water,  very  little  soluble 
in  ether,  cold  alcohol,  chloroform,  benzene,  readily  soluble  in  hot  alco- 
hol, chloroform  and  benzene,  fairly  soluble  in  cold  acetone,  easily  hot. 
The  mother  liquor  from  the  crystallization  from  alcohol  when  diluted 
with  water  gives  3-chloromercuri-2,  5-dimethyl  thiophene.  The  same 
substance  can  be  obtained  by  boiling  the  addition  compound  with  alco- 
hol for  some  time  and  cooling.  The  filtrate  from  the  mercuric  com- 
pound gives  tests  for  mercuric  ions. 

3-Chloromercuri-2,  5 -dimethyl- thiophene. 

Is  prepared  from  the  mercuric  chloride  addition  compound  by  long 
boiling  with  alcohol  and  cooling.  M.P.  156-7°,  after  sintering.  (SHg). 
It  is  insoluble  in  water,  slightly  soluble  in  cold  alcohol  easily  hot, 
fairly  soluble  in  cold  ether  and  benzene,  easily  soluble  in  acetone. 

T  Steinkopf  and  Bauermeister,  loc.  eft.  65, 


340  COMPOUNDS  OF  MERCURY 

The  chloride  reacts  with  sodium  iodide  even  in  excess,  giving  only  the 
corresponding  iodide  and  no  trace  of  the  R2Hg  compound.  This  be- 
haviour is  markedly  different  from  that  of  the  alpha  mercurated  com- 
pounds, which  tend  to  form  the  R2Hg  compound  even  when  only  one 
molecule  of  sodium  iodide  is  used.  The  R2Hg  compound  can  be  made 
from  the  (3-chloride  by  treatment  with  metallic  sodium  in  xylene. 

S-Iodomercwri-2,  5-dimethyl-thiophene. 

Prepared  from  the  chloride  in  acetone  solution  treated  with  sodium 
iodide.  It  crystallizes  from  benzene  in  white  needles.  M.P.  175°,  after 
sintering.  (Hg).  It  is  fairly  soluble  in  carbon  disulfide,  not  easily  in 
acetone,  little  in  ethyl  acetate  and  chloroform,  difficultly  in  carbon 
tetrachloride,  benzene  and  toluene,  easily  soluble  in  all  of  these  sol- 
vents hot.  Alcohol  does  not  dissolve  it  readily  even  on  heating. 

8,  S'-Mercuribis-2,  5-dimethyl-thiophene. 

It  cannot  be  prepared  from  the  chloride  and  an  excess  of  sodium 
iodide.  The  chloride  is  shaken  with  xylene  and  sodium  and  the  re- 
fluxed.  The  dark  residue  is  filtered  off  and  the  filtrate  is  evaporated 
to  a  small  volume.  A  brownish  white  residue  separates.  When 
purified  by  boneblack  and  crystallization  from  70-120°  ligroin  it  gives 
some  of  the  unchanged  chloride  and  a  very  small  amount  of  the  R2Hg 
compound.  M.P.  144-5°  (S). 

Mercury  Derivatives  of  Beta-substituted  Thiophenes.8 

&-Methylthiophene  reacts  with  mercuric  chloride  and  sodium  ace- 
tate forming  mono-  and  di-mercurated  products.  The  mercury  atoms 
enter  the  alpha  position.  It  has  not  been  determined  whether  the 
mono-product  has  the  mercury  on  the  same  side  of  the  ring  as  the 
methyl  group  or  not. 

5(f)-Chloromercuri-3-methyl-thiophene. 

Is  prepared  in  the  usual  way.  It  is  recrystallized  from  slightly  di- 
luted alcohol  to  separate  it  from  the  di-mercury  compound.  (CISHg) . 

2-5-Dichloromercuri-3-methyl-thiophene. 

A  by-product  in  preparation  of  the  mono  compound.  It  is  a  white 
granular  substance,  insoluble  in  common  solvents.  It  is  only  slightly 
attacked  by  acids,  even  by  concentrated  nitric  acid.  (CISHg). 

•Steinkopf,  Ann.  403  (1914),  15.     Volhard,  Ann.  267  (1892),  182. 


DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS      341 

fi-Isopropyl  thiophene  reacts  with  mercuric  chloride  and  sodium 
acetate  giving  a  mixture  of  mono-  and  di-mercurated  products  in  the 
ratio  of  two  to  one  by  weight. 

5(?)-Chloromercuri-2-isopropyl-thiophene. 

It  is  recrystallized  from  alcohol  in  which  the  di-compound  is  in- 
soluble. It  forms  white  needles  which  are  soluble  in  ether  and  insolu- 
ble in  water.  M.P.  137°  (CHClHg). 

2,  5-Dichloromercuri-3-isopropyl-thiophene. 

It  is  separated  from  the  mono-compound  by  extracting  the  latter 
with  hot  alcohol.  The  white  granular  residue  is  insoluble  in  all  common 
solvents.  It  is  only  slowly  attacked  by  nitric  acid.  (CHSClHg) . 

Mercury  Derivatives  of  Beta-disubstituted  Thiophenes.9 

3,  4-Dimethyl-thiophene  gives  a  mixture  of  mono-  and  di-mercurated 
products  in  the  ratio  of  two  to  one.    These  are  separated  by  hot  alco- 
hol which  does  not  dissolve  the  di-compound. 

2-Chloromercuri-3,  4- dimethyl- thiophene. 

Is  prepared  in  the  usual  way.  The  reaction  mixture  is  filtered 
after  fifteen  hours.  The  hot  alcohol  extract  gives  crystals  which  melt 
137-8°,  after  sintering.  (SHg).  It  is  only  very  slightly  soluble  in  hot 
water,  slightly  soluble  in  cold  alcohol,  benzene,  chloroform,  easily  on 
heating,  soluble  in  acetone  even  in  the  cold.  The  corresponding  iodide 
is  made  in  good  yield  from  the  chloride  by  one  molecule  of  sodium 
iodide  in  acetone.  None  of  the  R2Hg  compound  is  formed.  Crystalliza- 
tion from  benzene  gives  yellowish  leaflets.  M.P.  142°,  after  sintering. 
(SHg) .  It  is  easily  soluble  in  carbon  disulfide,  fairly  soluble  in  acetone 
and  chloroform,  difficultly  soluble  in  cold  benzene  and  toluene,  easily 
hot,  difficultly  in  alcohol. 

2,  2'-Mercwribis-3,  4- dimethyl- thiophene. 

Is  prepared  from  the  iodide  and  sodium  iodide  in  acetone.  Fair 
yield.  It  crystallizes  from  much  alcohol  in  felted  crystals.  M.P. 
155-6° ,  after  sintering.  (SHg).  It  is  easily  soluble  in  carbon  disulfide 
and  chloroform,  fairly  soluble  in  benzene  and  toluene,  little  in  cold 

"D.  R.  P.  247,625.  Chem.  Zentr.  1912  II  166.  Steinkopf  and  Bauermeister,  Ann. 
403  (1914),  63.  Steinkopf,  Ann.  413  (1917),  326.  Chem.  Abst.  11  (1917),  2326. 


342  COMPOUNDS  OF  MERCURY 

acetone,  easily  hot,  difficultly  in  cold  ligroin,  very  difficultly  in  cold 
alcohol,  fairly  hot. 

2,  5-Dichloromercuri~3,  4-dimethyl-thiophene. 

The  residue,  formed  in  the  preparation  of  the  mono-compound,  is 
purified  by  repeated  extractions  with  hot  alcohol.  It  is  insoluble  in 
common  solvents.  (SHg) .  It  does  not  melt  at  270°. 

Mercury  Compounds  of  the  Alkaloids. 

Almost  all  alkaloids  react  with  mercuric  chloride  and  other  mer- 
curic salts  forming  crystalline,  relatively  insoluble  compounds  which 
are  very  useful  in  the  separation  and  identification  of  these  substances. 
These  mercuric  compounds  are  probably  "molecular  addition  products." 
In  all  cases  hydrogen  sulfide  gives  the  griginal  alkaloid  and  mercuric 
sulfide. 

Mercury  Compounds  of  Pyridine  and  Belated  Substances. 

Many  addition  compounds  of  mercuric  salts  with  pyridine  and 
similar  substances  are  known.9a 

Mercury  Derivatives  of  Indole.10 

3- A  ce  toxymercuri-1  -me  thy  l-indole. 

Is  prepared  from  N-methyl  indole  and  mercuric  acetate.  It  crystal- 
lizes from  hot  alcohol,  benzene  or  acetone  in  fine  needles. 

3-Hydroxymercuri-  1-methy  l-indo  le . 

Is  insoluble  in  common  solvents,  soluble  in  alkalies.  Hot  mineral 
acids  split  the  C  —  Hg  linkage. 

3-Hydroxymercuri-8-p-anisyl-indole  is  a  brown  precipitate. 

A  compound  of  two  molecules  of  3-hydroxymercuri-2-methyl-indole 
and  one  molecule  of  mercuric  acetate  is  known.  It  forms  a  yellow  pre- 
cipitate, insoluble  in  common  solvents.  It  is  soluble  with  decompo- 
sition in  mineral  acids.  An  aqueous  suspension  is  only  gradually  black- 
ened by  hydrogen  sulfide.  This  is  remarkable  as  "molecular  com- 
pounds" of  this  kind  are  usually  blackened  immediately  by  sulfides. 

9a  See  Appendix  D. 

10  D.  R.  P.  236,893.     Chem.  Zentr.  1911  II  404. 


DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS      343 

2-Methyl  indole    (Methyl   ketole)    gives   a    complex   mercury    com- 
pound with  mercury  fulminate  and  hydrochloric  acid.11 

8-Acetoxymercuri-2-methyl-l-phthalyl-indole.12 

It  is  a  slightly  red  precipitate,  insoluble  in  common  solvents.  It 
is  decomposed  by  hot  dilute  mineral  acids. 

Quinoline  mercury  compounds. 

Mercury  salts  of  quinoline  sulfonic  acid,  carboxylic  acids,  and 
hydroxy  acids  are  heated  until  alkali  soluble.13 

Acridine. 

2,  7-Dimethyl-3,  6-diamino  acridine  treated  with  methyl  chloride 
and  mercuric  halides  gives  a  yellow  brown  powder  soluble  in  water, 
alcohol,  ethyl  acetate,  and  acetic  acid.14 

N-Methyl-2,  7-dimethyl-3,  6-diamino  acridine  reacts  with  mercury 
compounds  in  suitable  solvents  giving  a  yellow  brown  powder  soluble 
in  water,  alcohol,  and  insoluble  in  ether. 

Mercury  Derivatives  of  Pyrazolones.15 
H 


H— N  C=0 


H  —  C===C  —  H 

When  phenyl-5-pyrazolones  are  treated  with  mercuric  acetate  in 
alcohol  three  or  four  acetoxymercuri  groups  are  introduced  into  the 
molecule.  From  one  to  three  of  these  may  be  in  the  phenyl  group  de- 
pending on  the  conditions  and  the  other  substituents  in  the  pyrazolone 
ring.  Substitution  takes  place  in  the  benzene  ring  even  when  it  is  at- 
tached to  the  3  —  C  instead  of  the  1  —  N  of  the  ring.  The  other  ace- 
toxymercuri groups  are  attached  to  carbon  atoms  3  and  4.  In  most 
cases  one  of  the  groups  takes  the  place  of  the  hydrogen  on  the  4  —  C 


,  J.  prakt.lhem.  (2)  84  (1911),  211. 
2  D.  R.  P.  236,893  loc.  cit. 

3D.  R.  P.  289,246.     Chem.  Abst.  10   (1916),  2500. 
*U.  S.  Pat.  1,259,517.     Chem.  Altst.  12   (1918),  1496. 
8  Schrauth  and  Bauermeister,  Ber.  47  (1914),  2736. 


344  COMPOUNDS  OF  MERCURY 

and  the  other  together  with  an  alkoxyl  or  hydroxyl  group  adds  to  the 
double  bond  between  the  3  and  4  carbon  atoms.  If  the  original  pyra- 
zolone  has  no  hydrogen  atom  on  the  4  carbon  (the  carbon  alpha  to 
the  ketone  group),  mercuration  becomes  more  difficult.  It  is  impos- 
sible in  alcohol  solution  even  on  long  boiling.  This  perhaps  indicates 
that  substitution  in  the  4  position  precedes  a  shifting  of  the  entering 
group  to  the  benzene  nucleus.  If  the  group  in  the  4  position  is  a  halo- 
gen or  a  methyl  group,  mercuration  can  be  accomplished  by  heating 
the  pyrazolone  with  mercuric  acetate  at  160°.  Mercuration  then  takes 
place  in  the  benzene  ring  and  by  addition  of  —  HgOAc  and  —  OH  to 
the  3  and  4  positions  respectively.  If  the  4  position  is  occupied  by  a 
dimethylamino  group  no  mercuration  is  possible  as  the  mercuric  ace- 
tate oxidizes  the  compound  when  heated  with  it. 

3-Methyl-3,  4-dwcetoxymercuri-4-methoxy-l-acetoxymercuriphenyl-3, 

4-dihydr  o-5 -pyrazolone. 

3-Methyl-l-phenyl-5-pyrazolone  and  mercuric  acetate  are  mixed 
in  cold  methyl  alcohol.  The  rhombic  crystals  are  filtered  after  standing 
24  hours.  Yield  66%.  Additional  recovery  by  evaporating  the  mother 
liquor  in  vacuo  raises  the  yield  to  90%.  The  product  is  recrystallized 
from  methyl  alcohol.  The  crystals  contain  one  molecule  of  water 
which  can  be  removed  in  vacuo  at  the  boiling  point  of  xylene.  (CHHg, 
H20).  M.P.  167°,  with  slight  decomposition.  It  is  easily  soluble  in 
ethyl  alcohol,  soluble  in  ten  volumes  of  methyl  alcohol.  Treatment 
with  ammonium  sulfide  or  dilute  hydrochloric  acid  removes  the  mer- 
cury in  position  4,  leaving  the  mercury  in  position  3  and  that  attached 
to  the  benzene  ring. 

8-Methyl-3-chloromercuri-4-methoxy-l-chloromercuriphenyl-3,     4~di- 

hydro-5 -pyrazolone. 

It  is  prepared  by  treating  the  above  tri-acetoxymercuri  compound 
with  .25  N  hydrochloric  acid  which  removes  the  mercury  in  the  4  po- 
sition. It  is  somewhat  soluble  in  acetone.  (CHClHg) . 

3-Methyl-3,  4-diacetoxymercuri-4-methoxy-l-diacetoxymercuriphenyl- 
3,  4-dihydr o-5 -pyrazolone. 

It  is  prepared  from  the  same  3-methyl-l-phenyl-5-pyrazolone  and 
mercuric  acetate,  but  by  refluxing  in  methyl  alcohol  for  three  hours,  and 
then  evaporating  to  a  small  volume.  It  is  difficultly  soluble  or  entirely 
insoluble  in  the  common  solvents.  It  decomposes  about  225°  (CHHg) . 


DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS      345 

When  the  phenyl  group  is  attached  to  position  3  instead  of  to  po- 
sition 1  the  mercuration  takes  place  on  the  benzene  ring  and  the  4 
position  but  no  addition  of  —  HgOAc  and  —  OH  to  the  3,  4  positions 
takes  place.  The  change  in  the  position  of  the  phenyl  group  may 
cause  a  rearrangement  so  that  the  substance  is  a  5-hydroxy  pyrazole 
instead  of  a  5-pyrazolone. 

S-Diacetoxymercuriphenyl-4-acetoxymercuri-5-hydroxy  pyrazole. 

It  is  prepared  by  refluxing  3-phenyl-5-pyrazolone  with  three  moles 
of  mercuric  acetate  in  methyl  alcohol.  Any  cloudiness  is  removed  by 
adding  a  little  acetic  acid.  The  precipitate  obtained  on  cooling  is 
washed  with  methyl  alcohol  and  ether  and  dried  in  vacuo.  (CHHg). 
It  is  difficultly  soluble  in  ethyl  and  methyl  alcohols  and  in  acetic  acid. 
It  forms  colorless  needle  crystals.  Ammonium  sulfide  gives  mercuric 
sulfide.  Decomposes  at  250°.  Treatment  with  hydrochloric  acid  re- 
moves the  mercury  in  position  4  leaving  a  di-mercury  compound. 

S-Dichloromercuriphenyl-5-hydroxypyrazole. 

This  is  prepared  from  the  triacetoxymercuri  compound  and  .25 
N  hydrochloric  acid  which  removes  the  mercury  in  position  4.  (CHC1 
Hg).  It  is  insoluble  in  common  solvents.  It  decomposes  about  240° 
without  melting.  It  is  blackened  by  ammonium  sulfide  at  once.  This 
is  unusual  for  a  compound  containing  mercury  attached  to  a  phenyl 
group. 

2,  S-Dimethyl-3 ',   4-diacetoxymercwri-4-methoxy  -  1  -  acetoxymercuri- 
phenyl-3,  4-dihydro-5-pyrazolone. 

When  the  phenyldimethylpyrazolone  (antipyrine)  is  treated  with 
two  or  three  molecules  of  mercuric  acetate  no  manageable  product  is 
obtained.  Treatment  with  four  molecules  of  mercuric  acetate  at  60° 
gives  the  pure  tetramercurated  product.  Rhombic  leaflets.  Yield  97% 
(CHNHg).  It  sinters  about  205°  and  then  decomposes  giving  a  gas. 
It  is  insoluble  in  most  common  solvents  but  slightly  soluble  in  hot 
methyl  and  ethyl  alcohols,  especially  in  the  presence  of  a  trace  of 
acetic  acid.  It  is  more  soluble  in  water  acidified  with  acetic  acid,  very 
soluble  in  presence  of  mercurated  aromatic  amines,  ammonium  hy- 
droxide and  amine  bases  such  as  ethylenediamine.  Ammonium  sul- 
fide precipitates  the  mercury  in  position  4.  Hydrochloric  acid  re- 
moves this  mercury  leaving  the  tri-mercurated  product. 


346  COMPOUNDS  OF  MERCURY 

2,    3-Dimethyl-3-chloromercuri-4-methoxy-l-dichloromercuriphenyl-3, 

4-dihydro-5-pyrazolone. 

Prepared  from  the  tetra-acetoxymercuri  compound  and  .25  N  hy- 
drochloric acid  shaken  for  12  hours  to  remove  the  mercury  in  position 
4.  (CHClHg) .  The  microcrystalline  product  is  slightly  soluble  in  ace- 
tone, insoluble  in  common  solvents.  It  does  not  melt.  Ammonium 
sulfide  does  not  blacken  it  at  once.  The  filtrate  from  the  prepara- 
tion is  found  to  contain  one-quarter  of  all  the  mercury  originally  in 
the  tetramercurated  compound. 

2,  3 -Dimethyl- 3,  4-diacetoxymercuri-4-ethoxy-l-diacetoxymercuri- 
phenyl-S,  4-dihydro-5-pyrazolone. 

It  is  prepared  in  the  same  way  as  the  methoxy  compound  mentioned 
above  but  in  an  ethyl  alcohol  solution.  The  reaction  is  slower  than  in 
methyl  alcohol.  Yield  97%.  It  forms  fine  colorless  needles  contain- 
ing one  molecule  of  water  which  can  be  removed  over  phosphorus  pen- 
toxide  at  110°.  Its  solubilities  are  like  those  of  the  methoxy  com- 
pound. (CHHg) .  Hydrochloric  acid  as  usual  removes  the  mercury  in 
position  4. 

2,  8-Dimethyl-3,  4-diacetoxymercuri-4-methoxy-l-(diacetoxymercuri- 
p-tolyl)-3,  4-dihydro-5-pyrazolone. 

It  is  prepared  from  p-tolyl  dimethyl  pyrazolone  and  mercuric  ace- 
tate in  methyl  alcohol  at  60°  (CHHg) .  No  M.P.  Ammonium  sulfide 
gives  HgS  at  once.  Hydrochloric  acid  removes  the  4  mercuri  group. 

2)3-Dimethyl-3-chloromercuri-4-methoxy-l-(dichloromercuri-p-tolyl)-- 
3,  4-dihydr v-5 '-pyrazolone. 

The  tetra-mercuri  compound  is  treated  with  .25  N  hydrochloric 
acid.  (CHClHg) .  It  is  slightly  soluble  in  acetone  but  practically  in- 
soluble in  other  common  solvents.  It  is  not  blackened  at  once  by 
ammonium  sulfide. 

3  -  Methyl-  2-ethyl-3}  4  -  diacetoxymercuri-  4  -methoxy -1  -diacetoxymer- 

curiphenyl-3 ,  4-dihydro-5-pyrazolone. 

Phenyl  ethyl  methyl  pyrazolone  and  four  moles  of  mercuric  acetate 
are  heated  with  methyl  alcohol  at  60°  for  two  hours.  Prismatic  needles. 
Yield  95%  (CHHg) .  It  dissolves  readily  in  water  containing  a  trace  of 
acetic  acid  when  heated.  It  is  also  soluble  in  hot  methyl  and  ethyl 
alcohol  containing  acetic  acid.  It  is  practically  insoluble  in  other 


DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS      347 

common  solvents  but  is  very  soluble  in  ammonia  and  ethylenediamine. 
Decomposes  above  200°  without  melting.  Hydrochloric  acid  removes 
the  mercury  in  the  4  position. 

3  -  Methyl  -  2  -  ethyl  -  3-chloromercuri-4-methoxy-l-(dichloromercuri- 
phenyl-3,  4~dihydro-5 -pyrazolone. 

It  is  prepared  from  the  tetra-mercury  compound  and  .25  N  hydro- 
chloric acid  shaken  in  the  cold  for  12  hours.  The  yield  is  almost  quan- 
titative. (Hg). 

S-Methyl-2-ethyl-3,  4-diacetoxymercuri-4-methoxy-l-(diacetoxymer- 
curi-o-tolyl)-3,  4~dihydro-5-pyrazolone. 

Prepared  in  the  same  way  as  the  corresponding  phenyl  compound. 
(CHHg).  No  M.P.  It  reacts  in  the  usual  way  with  ammonium  sul- 
fide  and  HC1. 

3-Methyl-2-ethyl-3-chloromercuri-4  -  methoxy  -  1  -(dichloromercuri-o- 
tolyl)-3,  4-dihydr  o-5 -pyrazolone. 

It  is  prepared  from  the  tetra-mercury  compound  and  hydrochloric 
acid  in  the  usual  way.  (Hg) .  It  is  slightly  soluble  in  acetone  but  prac- 
tically insoluble  in  other  solvents.  Ammonium  sulfide  does  not  give 
HgS  at  once. 

2,  3,  4-Trimethyl-3-acetoxymercuri-4-hydroxy-l-triacetoxymercuri- 
phenyl-3,  4- dihydro-d -pyrazolone. 

The  phenyl  trimethyl  pyrazolone  cannot  be  mercurated  in  methyl 
alcohol  solution.  This  is  apparently  because  the  position  alpha  to 
the  ketone  group  has  no  hydrogen.  If  the  pyrazolone  and  four  moles 
of  mercuric  acetate  are  heated  without  any  solvent  in  an  oil  bath  at 
160°,  mercuration  takes  place.  The  cooled  product  is  extracted  with 
alcohol  and  decolorized  by  animal  charcoal.  It  is  obtained  as  a  color- 
less amorphous  hygroscopic  solid.  M.P.  237°  with  decomposition. 
(CHHg) .  Dilute  hydrochloric  acid  gives  a  tetrachloride.  Apparently 
only  mercury  in  the  4  position  is  easily  removed  by  acid.  Since  the 
original  mercury  compound  is  formed  by  adding  —  HgOAc  and  —  OH 
to  a  double  bond  it  is  unusual  that  acidification,  even  with  dilute  hy- 
drochloric acid,  does  not  regenerate  the  original  double  bond.  The 
tetrachloromercuri  compound  obtained  decomposes  at  245°  (Hg).  It 
gives  no  immediate  precipitate  with  ammonium  sulfide. 


348  COMPOUNDS  OF  MERCURY 

2,   3-Dimethyl-3-acetoxymercuri-4-bromo-4-hydroxy-l-triacetoxymer- 

curiphenyl-3 ,  4-dihydro-5-pyrazolone. 

The  absence  of  an  a-hydrogen  makes  an  easy  mercuration  impos- 
sible. If  the  phenyl-dimethyl-bromo-pyrazolone  is  heated  half  an 
hour  at  160°  with  four  moles  of  mercuric  acetate,  four  mercury  atoms 
are  introduced  into  the  molecule.  The  fusion  is  cooled  and  extracted 
with  alcohol,  decolorized,  and  precipitated  with  a  large  amount  of 
ether.  (CHHg).  It  is  very  hygroscopic,  easily  soluble  in  cold  water, 
less  soluble  in  methyl  alcohol  containing  a  little  acetic  acid.  It  decom- 
poses at  225°  giving  a  gas.  Cold  ammonium  sulfide  gives  no  reaction. 
On  boiling  it  gives  mercuric  sulfide.  Sodium  chloride  gives  the  tetra- 
chloromercuri  compound.  Sodium  hydroxide  gives  the  corresponding 
hydroxide.  This  compound  as  formulated  has  an  unusual  grouping  in 
the  4  carbon  which  has  a  bromide  atom  and  an  hydroxyl  group  at- 
tached to  it. 

3-M  ethyl- Jf.-acetoxymercuri-5-chlor  o-l  -phenyl-pyrazole. 

It  is  prepared  by  refluxing  phenyl-methyl-chloro-pyrazole  with 
three  molecules  of  mercuric  acetate  in  methyl  alcohol.  Total  yield 
97%.  It  crystallizes  from  chloroform  in  prisms.  (CHHg).  It  is 
easily  soluble  in  water,  alcohol  and  all  common  solvents  except  ether 
and  petrol  ether.  M.P.  123°.  Cold  ammonium  sulfide  gives  no  action. 
Sodium  chloride  and  sodium  hydroxide  give  the  corresponding  chlo- 
ride and  hydroxide. 

8-Methyl-4-chloromercuri-5-chloro-l -phenyl-pyrazole. 

It  is  prepared  from  the  acetate  by  sodium  chloride.  It  crystal- 
lizes from  acetone.  M.P.  165°.  It  is  readily  soluble  in  all  common 
solvents  except  ether  and  ligroin.  (CHClHg). 

Miscellaneous  references  on  antipyrine.16 

Phenylhydrazine  reacts  with  mercuric  oxide  giving  mercury  di- 
phenyl.17  Ethylhydrazine  gives  a  similar  reaction  forming  mercury 
diethyl. 

Mercury  Derivatives  of  Pyrimidine.18 

2,  6  -  Dihydroxy  -  4  -  imino  -  3,  4  -  dihydropyrimidine-3-acetic  acid 
changed  to  its  sodium  salt  and  treated  with  mercuric  salts  easily  gives 

38  Moulin,  Bull.  soc.  cMm.  (3)  29  (1903),  201.  Boehringer,  Chem.  Abst.  6  (1912), 
1500.  Scheftlin,  Chem.  Abst.  7  (1913),  2995.  Chem.  Abst.  13  (1919),  1126. 

17  B.  Fischer,  Ann.  199   (1879),  332.    Allen,  J.  Am.  Chem.  Soc.  25   (1903),  421. 

18  D.  R.  P.  224,491.     Chem.  Zentr.  1910  II  608. 


DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS      349 

a  compound  which  is  formulated  as  having  one  mercury  atom  in  place 
of  the  two  hydrogen  atoms  in  the  5  position.  This  grouping 
—  C  —  C  —  C  —  is  peculiar  enough  to  deserve  further  study. 


tt    4 


. 

Pyramidone  reacts  with  mercuric  chloride  giving  a  white  precipitate 
of  microcrystalline  needles.19 

2-Methyl-4-quinazolone. 

Gives  a  mercury  compound  when  treated  with  fuming  nitric  acid 
and  mercury  which  can  be  recrystallized  from  acetic  acid.  It  forms  a 
yellow  powder  which  does  not  melt  at  360°.  Insoluble  in  common  sol- 
vents. (N  for  C9H7ON2Hg).20 

Safranines  gives  complex  mercury  compounds.21 

These  do  not  react  with  sodium  hydroxide  and  give  only  a  slow 
action  with  ammonium  sulfide  on  heating. 

Acetoxymercuri  benzidine  is  obtained  as  a  white  amorphous  pow- 
der by  boiling  benzidine  and  mercuric  acetate  in  dilute  hydrochloric 
acid.21a  The  product  is  soluble  in  an  excess  of  dilute  acid. 

Acetoxymercuri  benzidine  sulfonic  acid  and  acetoxymercuri  benzi- 
dine disulfonic  acid  have  been  prepared  from  3-sulfobenzidine  and  3, 
3'-disulfobenzidine  heated  with  mercuric  acetate  in  water  solution.21* 

Cy  clomer  curipolymethylenes  ,22 

Substances  of  this  type  are  obtained  by  treating  dibromides  and 
di-iodides  with  dilute  sodium  amalgam.  The  products  are  usually  poly- 
merized forms  of  the  simple  compounds  in  which  mercury  is  part  of  a 
closed  ring.  This  tendency  to  polymerization  is  like  that  noted  in  an- 
alogous ring  compounds  containing  oxygen  or  sulfur.  The  mercury 
ring  compounds  are  harder  to  form  than  those  containing  oxygen  and 
sulfur.  Treatment  of  ethylene  halides  and  trimethylene  halides  with 
sodium  amalgam  gives  no  organic  mercury  compounds. 

1,  4-Diiodobutane  reacts  with  2%   sodium   amalgam  forming  a 

18  Weehuizen,  Chem.  Zentr.  1906  II  1628. 
2°Bogert,  J.  Am.  Chem.  Soc.  34  (1912),  530. 

21  D.  R.  P.  286,097.     Chem.  Z&ntr.  1915  II  569. 
2ia  private  communication,  G.   W.   Raiziss. 

22  v.  Braun,  Ber.  46  (1913),  1792.     Ililpert  and  Gruttner,  Ber.  47  (1914),  177,  IS'i, 
v.  Braun,  Ber.  47  (1914),  491. 


350  COMPOUNDS  OF  MERCURY 

polymer  of  cyclo-mercuri-tetramethylene.  1,  5-Dibromopentane  re- 
acts with  1%  sodium  amalgam  and  ethyl  acetate  giving  three  com- 
pounds having  the  composition  of  cyclo-mercuri-pentamethylene.  Com- 
pound 1  melts  at  120°  and  is  apparently  only  partly  polymerized. 
Compound  2  melts  at  41°  and  shows  a  molecular  weight  approxi- 
mately four  times  that  of  the  simple  compound.  Compound  3  is  an 
oil  having  a  molecular  weight  about  six  times  that  of  the  simple 
compound.  The  three  compounds  give  the  same  products  when  treated 
with  halogens  or  with  mercuric  halides. 


Polymerized  cyclomercuri-tetramethylene. 


It  is  formed  from  the  1,  4  diiodide  and  2%  sodium  amalgam  and 
ethyl  acetate.  The  product  is  easily  soluble  in  ether.  It  is  only  partly 
volatile  in  a  vacuum  at  170°.  It  decomposes  giving  metallic  mercury. 

CH2  —  CH2 
/  \ 

Cyclomercuri-pentamethylene,  Compound  1.  CH2  Hg. 

\  / 

CH2  — CH2 

The  crude  waxy  mixture  from  the  action  of  1%  sodium  amalgam 
on  the  dibromide  is  extracted  repeatedly  with  low  boiling  ligroin  which 
dissolves  compounds  1  and  3  leaving  compound  2  as  a  slightly  yellow 
fine  powder.  The  extracts  are  allowed  to  evaporate  spontaneously 
forming  a  large  amount  of  colored  oil  and  a  small  amount  of  compound 
1  as  white  crystals.  The  oil  on  standing  gives  a  small  amount  of  com- 
pound 2.  The  remaining  oil  is  compound  3.  Compound  1  melts  at 
120°.  It  is  recrystallized  from  a  mixture  of  equal  parts  of  benzene  and 
80°  ligroin.  It  forms  hard  snow  white  crystals.  (CHHg).  M.W. 
average  360,  calc.  270.  It  is  easily  soluble  in  cold  ether  and  low  boiling 
ligroin,  also  in  benzene,  difficultly  soluble  in  water.  Alcohol  changes 
it  to  a  smear  without  dissolving  it.  It  is  surprising  that  a  cyclo-mer- 
curi-pentamethylene should  be  a  solid  melting  at  120°.  The  formation 
of  a  ring  here  apparently  has  a  much  more  profound  effect  on  the 
physical  properties  than  it  has  in  the  case  of  oxygen,  carbon,  nitrogen 
or  sulfur  compounds. 


DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS      351 

By  analogy  to  these  compounds  it  would  be  expected  to  be  a  liquid 
boiling  at  about  210°  as  mercury  diethyl  boils  at  159°. 

/  CH2  — CH2 

/          /  \ 

Compound  2.      CH2  Hg 

V  \  / 

CH2  —  CH2 

The  residue  insoluble  ia  low  boiling  ligroin  is  dissolved  in  five 
volumes  of  benzene  at  35°,  filtered  and  overlay ed  with  twice  the  vol- 
ume of  absolute  ether  and  cooled  in  ice.  The  ether  which  evaporates 
is  replaced.  After  a  few  hours  a  fine  white  powder  separates  which 
can  be  further  purified  by  dissolving  in  100  volumes  of  hot  ether  and 
evaporating  in  vacuo  at  0°  to  one-quarter  volume.  The  product  is 
amorphous.  It  melts  sharply  at  41°,  gives  off  a  gas  at  120°  and  foams 
suddenly  at  124°  (CHHg).  M.W.  average  1130,  calc.  1080.  It  is  al- 
most insoluble  in  cold  ether  and  low  boiling  ligroin,  easily  soluble  even 
cold  in  chloroform,  benzene  and  its  homologs.  Absolute  alcohol  gives 
a  smear  without  dissolving  it. 

It  reacts  with  bromine  in  carbon  disulfide  forming  1,  5-dibromo- 
mercuripentane.  M.P.  150°  (CBrHg).  The  mother  liquor  gives  a 
small  amount  of  an  oil  containing  bromine  but  no  mercury.  This  is 
probably  pentamethylene  dibromide.  Treatment  with  iodine  in  ben- 
zene gives  a  similar  result.  1,  5-diiodomercuripentane.  M.P.  117°. 
White  needles.  (CHgl).  The  mother  liquor  gives  a  good  yield  of 
pentamethylene  diiodide. 

The  compound  reacts  in  benzene  with  ether  solutions  of  mercuric 
halides  giving  white  precipitates  of  the  corresponding  1,  5-dihalide- 
mercuri  pentanes.  These  are  washed  with  ether  and  crystallized  from 
benzene.  Chloride  M.P.  184°  (Cl.  &  mixed  M.P.).  Bromide  M.P.  150° 
(Br  &  mixed  M.P.).  Iodide  M.P.  117°  (I  &  mixed  M.P.). 

Compound  3.     [(CH2)5Hg]6. 

The  oil  obtained  from  the  petroleum  ether  extracts  of  the  crude  re- 
action product  of  pentamethylene  dibromide  and  sodium  amalgam  does 
not  crystallize  even  on  standing  for  weeks  in  a  vacuum  over  phosphorus 
pentoxide.  (C  high,  Hg  low).  M.W.  1780,  calc.  1620.  The  oil  prob- 
ably contains  impurities  which  do  not  contain  mercury.  It  reacts  with 
bromine,  iodine,  and  mercuric  halides  giving  the  same  compounds,  as 
those  obtained  from  compound  2. 


352  COMPOUNDS  OF  MERCURY 

Mer curation  of  Azo  Phenols  and  Azo  Naphthols.23 

If  the  position  ortho  to  the  phenolic  hydroxyl  is  open  treatment 
with  mercuric  acetate  introduces  the  acetoxymercuri  group.  If  both 
ortho  positions  are  open  it  is  possible  to  introduce  two  such  groups. 
Among  the  compounds  which  cannot  be  mercurated  even  when  fused 
with  mercuric  acetate  are  2-benzeneazo-6-bromo-4-methyl  phenol,  4- 
benzeneazo-2,  6-dibromo  phenol,  2-benzeneazo  -  4  -  methyl  -  6  -  bromo- 
phenol. 

Anhydro-%-hydroxymercuri-6-acetoxymercuri-4-benzemazo-phenol. 

The  diacetoxymercuri  compound  cannot  be  obtained  pure  as  it  loses 
acetic  acid  even  at  room  temperature.  At  120°  the  change  is  complete 
and  one  molecule  of  acetic  acid  is  removed  leaving  the  anhydride. 
The  product  from  refluxing  azophenol  with  mercuric  acetate  in  dilute 
acetic  acid  and  alcohol  is  dissolved  in  hot  acetic  acid  and  poured  into 
alcohol.  The  precipitate  is  dried  at  120°  (NHg).  It  does  not  melt 
at  300°.  It  is  insoluble  in  hot  water,  slightly  soluble  in  alcohol,  chloro- 
form, ethyl  acetate,  ethyl  benzoate,  benzene  and  nitrobenzene,  moder- 
ately soluble  in  pyridine,  readily  soluble  in  acetic  acid. 

2,  6-Dichloromercuri-4-benzeneazo-phenol. 

The  above  anhydro  compound  is  boiled  with  a  5%  potassium  hy- 
droxide and  filtered.  The  filtrate  is  treated  with  saturated  sodium 
chloride  solution  forming  an  orange  red  precipitate.  When  this  is 
digested  with  hydrochloric  acid  it  turns  brick  red.  (NClHg) .  It  does 
not  melt  at  300°.  It  is  insoluble  in  common  solvents,  but  slightly 
soluble  in  sodium  hydroxide.  It  does  not  react  with  benzene  diazonium 
chloride.  The  corresponding  dibromide  is  made  in  the  same  way  as  the 
chloride.  It  is  a  brown  red  precipitate  which  does  not  melt  at  300° 
and  is  insoluble  in  common  solvents.  (Br) .  No  definite  results  are  ob- 
tained by  treating  this  substance  with  bromine. 

2,  6-Diacetoxymercuri-4-tribromobenzeneazo-phenol 

It  is  prepared  from  the  azophenol  refluxed  for  six  hours  with  mer- 
curic acetate  in  dilute  acetic  acid  and  alcohol.  The  pink  precipitate 
is  recrystallized  from  acetic  acid.  (CHHgBrN).  It  does  not  melt  at 
300°.  It  is  very  difficultly  soluble  in  common  solvents,  soluble  in 

23  Smith  and  Mitchell,  J.  Chem.  Soc.  93  (1908),  845;  95  (1909),  1431.  Schamberg, 
Vhem.  A6«(.  11  (1917),  1690, 


DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS      353 

acetic  acid.    It  is  more  stable  than  the  corresponding  benzeneazo  com- 
pound but  loses  one  molecule  of  acetic  acid  if  heated  at  120°. 

8-Acetoxymercuri-4-methyl-6-benzeneazo-phenol. 

The  azophenol  is  treated  with  mercuric  acetate.  It  is  purified  by 
dissolving  in  acetic  acid  and  precipitating  fractionally  by  addition  of 
water.  M.P.  269-70°  (HgN).  The  compound  is  the  same  as  that 
obtained  from  p-cresol  mercuric  acetate  and  benzene  diazonium  chlo- 
ride.24 The  corresponding  chloride  is  obtained  by  treating  an  acetic 
acid  solution  of  the  acetate  with  sodium  chloride  solution.  It  recrystal- 
lizes  from  a  large  volume  of  alcohol  in  yellow  brown  needles.  M.P. 
246-8°  (HgCl). 

2-Acetoxymercuri-6-nitro-4-benzeneazo-phenol. 

Prepared  by  heating  the  azophenol  with  mercuric  acetate  in  dilute 
acetic  acid  and  alcohol  on  the  steam  bath  for  six  hours.  It  crystal- 
lizes from  acetic  acid  in  pale  yellow  microcrystals.  It  does  not  melt 
at  300°.  Insoluble  in  common  solvents  except  acetic  acid.  (NHg). 
The  corresponding  bromide  is  made  from  an  acetic  acid  solution  of  the 
acetate  and  potassium  bromide.  (Br) . 

The  reaction  of  mercuric  acetate  with  benzeneazonaphthols  is 
naturally  more  complicated  than  that  with  the  corresponding  azo- 
phenols.  l-Benzeneazo-(3-naphthol  gives  no  mercury  compound.  On 
fusion  with  mercuric  acetate  it  is  oxidized  to  a  (3|3'dinaphthyl  deriva- 
tive. 4-Benzeneazo-cc-naphthol  gives  a  similar  product  with  mercuric 
acetate.  When  2,  4-disubstituted-ct-naphthols  are  treated  with  mer- 
curic acetate  the  acetoxymercuri  group  is  introduced  into  the  mole- 
cule, probably  in  the  8  position.  The  combinations  of  substituents 
used  are  di-benzeneazo,  benzeneazo  and  nitro,  and  nitro  and  benzene- 
azo in  the  2  and  4  positions  respectively.  If  instead  of  the  benzeneazo 
group  a  tribromobenzeneazo  group  is  used  no  mercury  compounds  are 
obtained  probably  because  of  the  extreme  insolubility  of  the  original 
substances.  • 

8(?)-Acetoxymercuri-2,  4-dibenzeneazo-a-naphthol. 

It  is  insoluble  in  common  solvents.  Softens  at  218°,  melts  with 
decomposition  at  235-8°.  Acids  remove  the  mercury.  (CH) . 

"Dimroth.  Bar.  35  (1902),  2864. 


354  COMPOUNDS  OF  MERCURY 

8(?)-Acetoxymercuri-@-benzeneazo-4-nitro-a-naphthol. 

Red  amorphous  product.  M.P.  221-2°  decomp.  Insoluble  in  com- 
mon solvents.  (Hg) . 

8(?)'Acetoxymercuri-2-nitro-4-benzeneazo-a-naphthol. 

Brick  red  powder.  Soluble  in  hot  glacial  acetic  acid  which  re- 
moves part  of  the  mercury.  (CHNHg).  It  darkens  at  180°,  melts  at 
208°  with  decomposition.  The  corresponding  chloride  is  made  by  so- 
dium chloride.  It  is  insoluble  in  common  solvents.  It  darkens  at 
130°,  is  black  at  200°,  does  not  melt  at  270°. 

Reaction  of  Diazonium  Salts  with  Mercurated  Phenols  and 
Naphthols.25 

Mercurated  phenols  couple  with  diazonium  salts.  If  the  p-position 
is  unoccupied  the  mercury  in  the  ortho  position  remains  intact.  If, 
however,  the  mercury  is  in  the  para  position  the  coupling  takes  place 
there  and  the  mercury  is  eliminated.  Even  in  this  case  a  small  amount 
of  the  p-mercurated  compound  will  couple  in  the  ortho  position  leav- 
ing the  mercury  in  the  para  position.  The  splitting  off  of  the  mer- 
cury to  allow  the  coupling  is  suggestive  of  the  reaction  of  p-hydroxy- 
benzoic  acid  which  loses  carbon  dioxide  and  couples  in  the  para  po- 
sition when  treated  with  benzenediazonium  chloride.  The  reaction  of 
diazonium  salts  with  mercurated  phenols  is  sometimes  of  use  in  de- 
termining the  position  of  the  mercury  in  the  original  compound.  If 
the  coupling  results  in  the  elimination  of  the  organic  mercury,  the  lat- 
ter was  probably  originally  in  the  para  position.  o-Chloromercuri- 
phenol  couples  with  benzene  diazonium  chloride  giving  2-chloromer- 
curi-4-benzeneazo-phenol.  p-Chloromercuriphenol  gives  mainly  ben- 
zeneazophenol  and  mercuric  chloride  but  also  gives  a  small  amount  of 
4-chloromercuri-2-benzeneazo-phenol.  2,  4-Dichloromercuriphenol  has 
half  of  its  organic  mercury  removed  forming  2-chloromercuri-4-ben- 
zeneazo-phenol.  Diazotized  m-aminophenyl  malachite  green  couples 
with  o-chloromercuriphenol  but  no  pure  product  is  obtained.  2,  6-Di- 
chloromercuri-4-benzeneazo-phenol  will  not  react  with  benzene  diazo- 
nium chloride.  2-Acetoxymercuri-p-cresol  couples  in  the  free  ortho 
position  giving  2-acetoxymercuri-6-benzeneazo-p-cresol.  The  chloride 
of  this  compound  is  obtained  by  precipitating  by  sodium  chloride.  It 

2BDimroth,   Chem.   Zentr.   1901    I   450.      Ber.   35    (1902),    2044,    2860.      Smith  and 
Mitchell,  loc.  cit.  848.     Reitzenstein  and  Bonitsch,  J.  prakt.  Chem.   (2)   86   (1912),  80. 


DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS      355 

crystallizes  from  much  alcohol  in  fine  yellow  brown  needles  which 
gradually  darken  and  melt  at  249°,  with  decomposition.  It  is  rather 
difficultly  soluble  in  alcohol,  ether  and  benzene.  (NCI). 

A  solution  of  an  alkali  salt  of  hydroxymercurisalicylic  acid  reacts 
with  diazonium  salt  solutions  in  the  cold  giving  water  soluble  com- 
pounds.26 

Benzene  diazonium  chloride  reacts  with  an  alkaline  solution  of 
1-acetoxymercuri-p-naphthol  giving  inorganic  mercury  and  1-benzene- 
azo-p-naphthol.  Diazotized  p-nitroaniline  gives  a  similar  reaction. 
The  corresponding  mercurated  6-sulfonic  acid  gives  no  action  with 
ammonium  sulfide  but  as  soon  as  treated  with  a  diazonium  salt  solu- 
tion it  gives  mercuric  sulfide  showing  that  inorganic  mercury  has  been 
liberated  and  that  coupling  has  probably  taken  place.  The  anhydride 
of  l-hydroxymercuri-4-carboxy-p-naphthol  couples  with  diazosulfan- 
ilic  acid  in  the  1 -position  liberating  inorganic  mercury. 

l-Hydroxymercuri-(3-naphthylamine-6-sulfonic  acid  does  not  re- 
act with  ammonium  sulfide  but  as  soon  as  it  is  treated  with  diazo- 
sulfanilic  acid  it  forms  a  dye  and  a  solution  which  immediately  gives 
mercuric  sulfide  with  sulfides. 

Products  Obtained  by  Diazotizing  Mercurated  Amines.27 

o-Mercuribis-p-aminobenzoic  acid  can  be  diazotized  and  boiled 
in  water  solution  to  form  the  corresponding  phenol,  o-mercuribis-p- 
hydroxybenzoic  acid.  p-Acetoxymercuri  aniline  can  be  diazotized  and 
coupled  with  a  variety  of  aromatic  compounds. 

p-Acetoxymercuri-benzeneazo-phenol. 

Diazotized  p-acetoxymercuri  aniline  is  treated  with  two  molecules 
£>f  phenol  in  10%  sodium  hydroxide.  After  standing  twelve  hours  the 
mixture  is  salted  out  with  sodium  acetate.  The  solid  is  dissolved  in 
dilute  sodium  hydroxide  and  precipitated  by  acetic  acid  and  then 
crystallized  from  acetic  acid.  It  forms  orange  crystals  melting  at  218° 
(HgN) .  The  alkaline  solution  dyes  silk  light  yellow. 

p-Acetoxymercuri-benzeneazo-resorcin. 

It  forms  a  very  insoluble  dark  brown  powder.  It  darkens  at  160° 
and  decomposes  about  190°  (HgN).  An  alkaline  solution  dyes  silk 
orange. 

23  D.  R.  P.  800,561.     Frankel,  665. 

27  Blumenthal  and  Oppenheim.  'Biochetri.  Z.  39  (1912),  51.  Jacobs  and  Heid&l- 
berger,  Jf  Piol.  CTrieiA,  20  (1915),  516. 


356  COMPOUNDS  OF  MERCURY 

p-Acetoxymercuri-p'-dimethylamino-azobenzene. 

It  is  prepared  by  coupling  the  diazotized  mercurated  aniline  with 
an  acetic  acid  solution  of  dimethylaniline.  It  crystallizes  from  amyl 
alcohol  in  small  brick  red  crystals.  M.P.  215°.  An  acetic  acid  solu- 
tion dyes  silk  bright  yellow.  It  is  difficultly  soluble  in  common  sol- 
vents except  acetic  acid  which  gives  a  bright  red  solution.  (HgN) .  The 
corresponding  diethylamino  compound  is  made  in  a  similar  way.  Re- 
crystallized  from  absolute  alcohol  it  forms  glistening  orange  brown 
plates.  It  is  more  soluble  than  the  dimethylamino  compound.  It  turns 
red  at  120°  and  melts  at  154.5-156°  I  HgN  I. 

l-amino-2-(p-acetoxymercuri  benzeneazo)-5-napthalene  sulfonic  acid. 
Is  prepared  by  coupling  diazotized  p-acetoxymercuri  aniline  with 
a-naphthylamine-5-sulfonic  acid.    It  decomposes  about  280°  (Hg) . 

(p-Acetoxymercuri-o-methylbenzeneazo) phenol. 

It  is  prepared  from  diazotized  p-acetoxymercuri-o-toluidine  and 
phenol.  It  is  recrystallized  from  85%  alcohol  containing  a  trace  of 
acetic  acid.  On  rapid  heating  it  melts  at  205.5-6°  (corr.),  after  soften- 
ing. (HgN). 

Mercuric  salts  and  diazonium  salts  form  stable  double  compounds.28 

Albumen  Compounds  of  Mercury. 

Hemin  mercury  compounds.29  Mercury  compounds  formed  from 
horse  hemoglobin  and  mercuric  salts  are  soluble  in  dilute  ammonium 
hydroxide  and  even  in  very  dilute  ammonium  sulfide  solution.  They 
are  less  soluble  in  ammonium  carbonate  and  sodium  hydroxide. 

Mercury  compounds  of  nucleic  acids.30 

Mercury  Derivatives  of  Aromatic  Arsenicals.31 

Many  of  the  arsonic  acids  of  aniline  and  phenol  and  their  substi- 
tution products  have  been  mercurated  in  the  usual  way.  In  most  cases 
the  structures  assigned  to  the  products  have  not  been  confirmed  experi- 

28IIantzsch,  Ber.  28  (1895),  1736. 

29  Ohem.  Zentr.  1914  II  1447. 

30  Realenzyk.  Pharm.  VI  486.     Blumenthal  and  Oppenbeira,  Biochem.  Z.  57  (1913), 
288. 

31  Morgan,  "Organic  Compounds  of  Arsenic  and  Antimony,"  1918,  p.  183  ff.     Bert- 
heim,   "Handbuch   der    organischen  Arscnverbindungcn,"    1913,   p.    132    ff.      Brit.    Pat. 
12,472.     (1908).     Raiziss,  Kolmer  and  Gavron,  J.  Biol.  Chem.  40  (1919),  533. 


I 
DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS      357 

mentally.  However,  they  are  probably  correct  as  most  of  the  com- 
pounds which  have  been  mercurated  have  positions  ortho  to  the  amino 
or  hydroxyl  group  which  are  open.  In  all  probability  the  acetoxy- 
mercuri  group  enters  this  position. 

Arsanilic  acid  when  treated  with  mercuric  acetate  and  then  with 
sodium  hydroxide  gives  sodium  salts  of  the  acids,  3-hydroxymercuri-4- 
aminophenyl  arsonic  acid  and  3,  5-dihydroxymercuri-4-aminophenyl 
arsonic  acid.  Treatment  with  sodium  chloride  gives  the  correspond- 
ing chlorides  which  are  less  soluble  than  the  hydroxides.32 

3-Acetoxymercuri-4-benzylaminophenyl  arsonic  acid  forms  a  pale 
yellow  amorphous  powder.  It  is  soluble  in  dilute  alkali.32a 

3-Acetoxymercuri-4-benzylamino-5-nitrophenyl  arsonic  acid  sepa- 
rates as  a  yellow  amorphous  substance  on  heating  solutions  of  mercuric 
acetate  and  the  sodium  salt  of  the  benzylamino-nitrophenyl  arsonic 
acid.32a 

The  arsonic  acid  of  o-toluidine  gives  3-hydroxymercuri-4-amino-5- 
methylphenyl  arsonic  acid.33  This  arsonic  acid  also  gives  a  complex 
compound  which  has  received  the  name  "Hydryl"  and  is  believed  to 
have  the  formula, 

NH-  -Hg-  -NH 

HOHg  -  /\  -  CH3  CH3  -  /\  -  HgOH 


As03Na2  AsO3Na2 

Apparently  the  positions  of  the  mercury  groups  has  not  been 
proved.34 

The  arsonic  acid  obtained  from  o-nitroaniline  reacts  with  mer- 
curic acetate  giving  3-acetoxymercuri-4-amino-5-nitrophenyl  arsonic 
acid.35  This  substance  is  soluble  in  acetic  acid,  10  per  cent  hydro- 
chloric acid,  slightly  soluble  in  methyl  alcohol,  insoluble  in  ethyl  alco- 
hol, ether,  and  methyl  acetate.  It  reacts  with  ammonium  sulfide  giving 
an  immediate  precipitate  of  mercuric  sulfide. 

The  arsonic  acid  of  o-bromoaniline  gives  3-acetoxymercuri-4-am- 
ino-5-bromophenyl  arsonic  acid35  It  is  soluble  in  sodium  hydroxide, 

32  Brit.  Pat.,  loc.  cit. 

sza  Private  communication,   G.  W.   Raiziss. 

33  Brit.  Pat,  loc.  cit. 

"  Jowett,  see  Morgan,  loc.  cit.  184. 
86  Raiziss  et  al.f  loc.  cit. 


358  COMPOUNDS  OF  MERCURY 

10  per  cent  hydrochloric  acid,  and  warm  acetic  acid.  It  reacts  with 
cold  ammonium  sulfide.  The  corresponding  oxalyl  compound  has  been 
prepared. 

p-Hydroxyphenyl  arsonic  acid  when  treated  with  mercuric  acetate 
and  then  with  sodium  hydroxide  gives  a  salt  of  3,  5-dihydroxymercuri- 
4-hydroxyphenyl  arsonic  acid.56 

The  arsonic  acid  of  o-cresol  gives  3-hydroxymercuri-4-hydroxy-5- 
methylphenyl  arsonic  acid.37 

The  arsonic  acid  of  o-nitrophenol  gives  3-acetoxymercuri-4-hy- 
droxy-5-nitrophenyl  arsonic  acid.58  It  .is  soluble  in  sodium  hydroxide, 
insoluble  in  methyl  alcohol,  ethyl  alcohol,  ether,  methyl  acetate,  and 
acetic  acid.  It  does  not  react  at  once  with  cold  ammonium  sulfide 
but  does  give  mercuric  sulfide  after  thirty  minutes. 

The  position  of  the  mercury  in  this  compound  is  proved  by  treat- 
ment with  iodine  in  potassium  iodide  solution.  This  gives  3-iodo-4- 
hydroxy-5-nitrophenyl  arsonic  acid.  If  the  mercury  compound  is 
treated  with  a  rather  concentrated  sodium  sulfide  solution  it  is  con- 
verted to  3,  3'-mercuribis-4-hydroxy-5-nitrophenyl-arsonic  acid.  So- 
dium stannite  is  used  as  a  reagent  to  test  the  completeness  of  the 
"bridging"  reaction  as  it  does  not  react  with  the  R2Hg  compound  but 
gives  a  precipitate  of  mercury  if  any  of  the  R  —  Hg  —  X  compound 
remains.39 

The  arsonic  acid  of  o,  o'-dinitrophenol  gives  a  mercury  compound 
which  is  formulated  as  2-acetoxymercuri-3,  5-dinitro-4-hydroxyphenyl 
arsonic  acid.  It  is  partly  soluble  in  sodium  hydroxide,  insoluble  in 
methyl  alcohol,  ethyl  alcohol,  ether,  and  methyl  acetate.  It  gives  mer- 
curic sulfide  at  once  with  cold  ammonium  sulfide.40 

The  arsonic  acid  of  o-aminophenol  gives  3-acetoxymercuri-4-hy- 
droxy-5-aminophenyl  arsonic  acid.  It  is  soluble  in  sodium  hydroxide 
with  decomposition.  It  is  slightly  soluble  in  acetic  acid  and  10  per  cent 
hydrochloric  acid.  It  is  insoluble  in  other  solvents.40  It  does  not 
give  mercuric  sulfide  until  digested  with  ammonium  sulfide  for  thirty 
minutes  at  80°. 

The  arsonic  acid  of  o-acetaminophenol  gives  3-acetoxymercuri-4- 
hydroxy-5-acetaminophenyl  arsonic  acid.40&  (N).  It  forms  a  brown 

88  Brit.  Pat.,  loc.  cit. 

« lUd. 

88  Raiziss  et  al.,  loc.  cit. 

"Stieglitz,  Kharasch,  and  Hanke,  J.  Am.  Ghem.  Soc.  43    (1921),  1185. 

40  Raiziss  et  al.,  loc.  cit. 

«>a  private   communication,    G.    W.    Raiziss. 


DERIVATIVES  OF  HETEROCYCLIC  COMPOUNDS     359 

amorphous  mass  which  is  soluble  in  dilute  sodium  hydroxide  but  is  in- 
soluble in  the  usual  organic  solvents  and  in  dilute  acids. 

The  arsenic  acid  of  o,  o'-diaminophenol  gives  2-acetoxymercuri-3, 
5-diamino-4-hydroxyphenyl  arsonic  acid.  This  resembles  the  corre- 
sponding compound  from  o-aminophenol.  It  reacts  with  ammonium 
sulfide  only  on  heating  at  80°  for  thirty  minutes.41 

p-Benzarsonic  acid  gives  a  compound  containing  one  acetoxymer- 
curi  group.  It  has  not  been  determined  whether  this  group  is  ortho 
to  the  carboxyl  group  or  to  the  arsonic  acid  group.  The  compound 
is  soluble  in  dilute  hydrochloric  acid,  concentrated  sodium  chloride 
solution,  insoluble  in  sodium  hydroxide  and  organic  solvents.  It  gives 
mercuric  sulfide  at  once.41 

The  azo  compounds  obtained  from  the  diazotized  arsonic  acid  of 
o-toluidine  and  phenol  or  dimethyl  aniline  have  been  mercurated  form- 
ing the  compounds, 


CH 


H2OaAs  -<-          V-  N  =  N  -<(          V-  OH 

and 
HAAs-/          \_N  =  N-<          >-N(CH3); 


«  Raiziss  et  al.,  loc.  cit. 
42  Brit.  Pat.,  loc.  cit. 


APPENDIX  A. 

Analysis  of  Organic  Mercury  Compounds. 

I.    Analysis  for  Mercury. 
A.    Determination  as  the  metal. 

1.  Collection   of  mercury   during   the   analysis   for  carbon   and 
hydrogen.1 

The  original  device  was  to  constrict  the  combustion  tube  in  two 
places  and  condense  the  mercury  in  the  space  between  them.  After 
the  combustion  this  piece  of  tubing  was  broken  off,  weighed,  freed  from 
mercury  by  heating,  and  weighed  again.  Grignard  and  Abelmann  im- 
proved this  arrangement  by  using  a  separate  tube  containing  gold  foil 
or  fine  wire  to  catch  the  mercury.  Gold  coated  asbestos  has  been 
recommended  for  this  purpose.  (Werder.) 

2.  Collection  of  mercury  from  the  substance  heated  with  lime,  etc.2 
In  this  method  the  compound  to  be  analyzed  is  mixed  with  lime, 

magnesite,  sodium  carbonate  and  similar  substances.  The  metallic 
mercury  is  distilled  out  in  various  ways  and  condensed  in  constricted 
tubes,  tubes  containing  gold  foil,  or  on  gold  surfaces  of  various  kinds. 
The  method  used  in  the  writer's  laboratory  involves  the  condensation 
of  the  mercury  on  the  inside  of  a  specially  designed  gold  crucible.3 

3.  Collection  of  mercury  formed  by  the  action  of  metallic  so- 
dium and  alcohol.4 

Some  organic  mercury  compounds  when  dissolved  in  alcohol  react 
with  metallic  sodium  or  with  the  hydrogen  formed  from  its  action  on 
the  alcohol  giving  metallic  mercury.  The  globule  of  mercury  is  col- 
lected, washed,  dried,  and  weighed  in  the  usual  way. 

JA.  W.  von  Hofmann,  Ann.  47  (1843),  63.  Frankland  and  Duppa,  J.  Chem.  Soc. 
16  (1863),  415.  Ann.  130  (1864),  107.  Erdmann  and  Marchand,  J.  prakt.  Chem.  (2) 
31  (1885),  393,  Grignard  and  Abelmann,  Bull.  soc.  cMm.  (4)  19  (1916),  25.  Chem. 
Abst.  10  (1916),  1486  (cut  of  apparatus).  Werder,  Z.  anal.  Chem.  39  (1900),  358. 

2Wertheim,  Ann.  51  (1844),  304.  Brandis,  Ann.  66  (1848),  269.  Hinterberger, 
Ann.  82  (1852),  317.  Hofmann,  Ber.  31  (1898),  1907;  32  (1899),  878;  33  (1900), 
1335  ;  33  (1900),  1347,  1355,  1361,  2699.  Sand,  B&r.  34  (1901),  1338.  Werder,  Z.  anal. 
Chem.  39  (1900),  358. 

8  See  below. 

*Schoeller  and  Schrautb,  Ber.  53   (1920),  641. 

361 


362  COMPOUNDS  OF  MERCURY 

4.  Formation  of  the  metal  by  direct  electrolysis  of  a  solution  of 
the  organic  mercury  compound.5 

A  few  organic  mercury  compounds  which  are  soluble  in  alkali  can 
be  electrolyzed  directly  in  alkaline  solution.  Of  course  the  organic 
compound  can  be  decomposed  by  acid  and  the  resulting  solution  can 
be  electrolyzed. 

B.  Determination  of  mercury  by  iodimetry.6 

C.  Determination  of  mercury  by  precipitation  methods. 

The  organic  mercury  compound  must  first  be  decomposed  to  give 
inorganic  mercuric  salts.  The  method  of  treatment  depends  on  two 
things,  (a)  the  stability  of  the  C  —  Hg  linkage,  and  (b)  the  nature 
of  the  organic  residue  left  after  the  decomposition.  In  some  cases 
warming  with  dilute  acid  will  remove  all  of  the  mercury  in  inor- 
ganic form.  In  others  vigorous  treatment  with  acid  oxidizing  agents  is 
necessary.  In  extreme  cases  the  mercury  compound  must  be  decom- 
posed by  fuming  nitric  acid  in  a  sealed  tube  at  a,  high  temperature. 
This  process  must  be  used  carefully  as  some  organic  mercury  com- 
pounds decompose  explosively  in  contact  with  the  nitric  acid.  In 
these  cases  it  is  advisable  to  heat  the  tubes  in  vertical  position  for 
some  hours  so  that  the  decomposition  takes  place  without  actual  con- 
tact between  the  substance  and  the  liquid  acid.  After  this  preliminary 
heating  the  tubes  are  allowed  to  cool  and  then  heated  in  the  usual 
horizontal  position.7  Unless  the  organic  products  are  completely  oxi- 
dized they  may  interfere  with  the  precipitation  or  may  contaminate  the 
precipitate  formed.  In  some  cases  mercuric  sulfide  may  be  freed  from 
such  impurities  by  extraction  with  pyridine.8  Among  the  oxidizing 
agents  used  are  the  following:  nitric  acid,  aqua  regia,  bromine  water, 
acid  permanganate,  and  acid  dichromate.9 

The  solution  resulting  from  the  decomposition  contains  inorganic 
mercury  which  can  be  determined  by  any  of  the  usual  methods.  The 
purification  of  the  mercuric  sulfide  precipitate  by  extraction  with 
pyridine  has  been  mentioned.  The  filtration  of  the  mercuric  sulfide 

0  Sand  and  Singer,  Ber.  (1902),  3170. 

•Sakurai,  J.  Ohem.  Soc.  37  (1880),  658.     Brieger,  Chem.  Zentr.  1912  I  753. 

'Hilpert  and  Griittner,  Ber.  48  (1915),  911. 

"Manchot,  Ann.  421  (1920),  321. 

•Gerhardt,  Ann.  80  (1851),  111.  Hofmann,  Ber.  31  (1898),  1905.  Hofmann  and 
Sand,  Ber.  33  (1900),  1350,  2697.  Rupp  and  Kropat,  Apoth.  Ztg.  1912,  p.  377.  Brieger 
and  Schulemann,  J.  prakt.  Chem.  (2)  89  (1914),  131.  Hilpert  and  Gruttner,  loc.  cit. 
Whitmore,  J.  Am.  Chem.  Koc.  41  (1919),  1848.  Schoeller  and  Schrauth,  Ber.  53  (1920), 
634.  White,  J.  Am.  Chem.  Soc.  42  (1920),  2359. 


APPENDIX  A  363 

is  facilitated  by  having  a  piece  of  quantitative  filter  paper  under  the 
asbestos  matte  in  the  Gooch  crucible.10  The  inorganic  mercury  solu- 
tion may  be  treated  with  a  zinc  thiocyanate  solution  to  precipitate 
the  complex  thiocyanate  of  zinc  and  mercury.11 

II.  Analysis  for  Halogens. 

A.  After  decomposition  of  the  organic  mercury  compound  in  solu- 
tion. 

Of  course  the  halogen  cannot  be  determined  by  any  of  the  usual 
methods  until  the  mercury  has  been  removed  from  the  solution.  If 
this  is  done  by  precipitation  as  the  sulfide  the  halogen  may  be  deter- 
mined in  the  filtrate  in  the  usual  way.12 

B.  After  decomposition  by  heating  the  solid  mercury  compound 
with  lime,  etc. 

The  decomposition  mixture  from  which  mercury  has  been  removed 
by  distillation  is  treated  with  nitric  acid  and  precipitated  by  silver 
nitrate  with  the  usual  precautions.13 

C.  After  treatment  with  hot  sodium  carbonate  solution. 

In  some  cases  the  organic  mercury  compound  can  be  boiled  with 
sodium  carbonate  and  the  halogen  can  be  determined  in  the  filtrate  by 
the  method  of  Volhard.  This  method  is  successful  only  when  the 
mercury  remains  in  the  precipitate  either  in  the  form  of  the  oxide  or 
an  insoluble  organomercuric  oxide.  The  fact  that  many  of  these 
substances  are  water  soluble  limits  this  method.14 

III.  Analysis  for  Carbon  and  Hydrogen. 

The  combustion  of  organic  mercury  compounds  must  be  carried 
out  in  such  a  way  that  the  mercury  is  completely  removed  before  the 
combustion  products  reach  the  absorption  train.  This  is  probably 
best  done  by  means  of  the  device  of  Grignard  and  Abelmann.15  If  it  is 
not  desired  to  determine  the  mercury  quantitatively  it  may  be  re- 
tained by  gold  foil,  leaf,  wire,  or  gold  coated  asbestos  in  the  end  of 
the  combustion  tube  itself.  Another  device  is  to  use  a  long  combustion 

10  White,  loc.  cit. 

"Hart  and  Hirschf elder,  J.  Am.  Chem.  Soc.  42  (1920),  2684. 

12  Kutscheroff,  Ber.  17  (1884),  14.  Z.  anorg.  Chem.  14  (1898),  326.  Whitmore, 
loc.  cit. 

18  Pringsheim,  Ber.  41  (1908),  4267.  Kohn  and  Ostersetzer,  Z.  anorg.  Chem.  80 
(1913),  218.  Schrauth  and  Bauerschmidt,  Ber.  47  (1914),  2740.  Lederer,  Ber.  47 
(1914),  279. 

"Biilmann,  Ber.  33  (1900),  1648. 

"Loc.  cit. 


364  COMPOUNDS  OF  MERCURY 

tube  in  two  furnaces  witli  a  cooler  section  between  in  which  the  mer- 
cury condenses.16 

IV.  Analysis  for  Acetate. 

Since  mercuric  acetate  is  the  commonest  mercurating  agent  the 
determination  of  the  acetate  group  is  often  useful.  This  is  done  by 
treatment  with  phosphoric  acid  followed  by  steam  distillation.  The 
acetic  acid  in  the  distillate  is  titrated.17 

V.  There  are  also  a  number  of  articles  on  the  general  analysis  of  mer- 
cury compounds.18 

18  Gerngross  and  Kersasp,  Ann.  406  (1914),  247.  Miscellaneous  references  on  the 
combustion  of  organic  mercury  compounds.  Nicholson,  J.  Chem.  Soc.  3  (1851),  321. 
Ann.  62  (1847),  79.  Dunhaupt,  J.  prakt.  Chem.  (1)  61  (1854),  399.  Frankland  and 
Duppa,  Ann.  130  (1864),  107.  Cowper,  J.  Chem.  Soc.  39  (1881),  242.  Erdmann  and 
Marchand,  J.  prakt.  Chem.  (2)  31  (1884),  393.  Dimroth,  Ber.  32  (1899),  759.  Sand 
and  Gensslef,  Ber.  36  (1903),  3706.  Anschiitz,  Ann.  359  (1908),  202.  Schoeller, 
Schrauth,  and  Struensee,  Ber.  44  (1911),  1048.  Hilpert  and  Griittner,  Ber.  48  (1915), 
911.  Manchot  and  Haas,  Ann.  399  (1913),  135.  Gerngross  and  Kersasp,  loc.  cit. 
Grignard  and  Abelmann,  loc.  cit. 

17  Brieger  and  Schulemann,  loc.  cit.     White,  J.  Am.  Chem.  Soc.  42   (1920),  2355. 

18  Z.  analyt.  Chem.  17  (1878),  526;  39  (1900),  358;  40  (1901),  534.     Compt.  rend. 
116  (1893),  584.     Bull.  soc.  chim.   (3)   9   (1893),  504.     &melin-Kraut-Friedtieim-Peter8 
Handbuch  d.  cunorg.  Chem.  V-II  462.     Chem.  Ztg.  Rep.  10   (1886),  216.     J.  Chem.  Soc. 
87   (1905),  431,  1878;  103    (1913),  513.     Analyst,  Oct.,  1919.     J.  Ind.  Eng.   Chem.  2 
(1910),  481.     Chem.  Abst.  7   (1913),  536,  896,  3979;  12   (1918),  739.     Ber.  38   (1905), 
2209.     Biochem.  Z.  36  (1911),  291.     Chem.  Zentr.  1889  II  391;  1911  II  722;  1912  II 
151. 


APPENDIX  A  365 

Determination  of  Mercury  as  the  Metal. 


G/ass  Ceafer 


Gc/d  Cruc/bfe 


The  method  for  the  determination  of  mercury  in  organic  compounds 
which  has  proved  most  satisfactory  in  the  author's  laboratory  is  a 
modification  of  the  ordinary  method  of  heating  the  compound  with  lime 
and  collecting  the  metallic  mercury.19  The  only  disadvantage  is  the 
initial  cost  of  the  gold  crucible.  However,  the  method  is  so  much 
more  rapid  than  the  ordinary  methods  of  determining  mercury  that  the 
time  saved  warrants  the  expense. 

Apparatus. 

As  shown  in  the  accompanying  diagram  the  apparatus  consists  of  a 
gold  crucible  and  an  iron  crucible  each  with  a  flange  at  the  mouth. 

19  The  apparatus  was  designed  and  the  details  of  the  process  were  worked  out  by 
Mr.  V.  E.  Mebarg,  Research  Assistant,  under  a  grant  from  the  U.  S.  Interdepartmental 
Social  Hygiene  Board,  Dr.  T.  A.  Storey,  Secretary. 


366  COMPOUNDS  OF  MERCURY 

The  iron  crucible  must  be  slightly  smaller  at  the  mouth  than  the  gold 
crucible.  The  two  crucibles  are  held  together  by  two  heavy  iron 
rings  which  are  drawn  tightly  together  by  four  screws.  The  dimen- 
sions given  in  the  diagram  give  a  gold  surface  sufficient  for  the  accu- 
rate amalgamation  of  quantities  of  mercury  up  to  0.12  gm.  The  di- 
mensions indicated  need  not  be  exactly  copied  except  the  difference 
between^  the  mouth  diameters  of  the  crucibles.  As  has  been  mentioned 
the  iron  crucible  must  be  slightly  smaller.  If  this  is  not  the  case  there 
will  be  losses  of  mercury  by  its  vapor  working  into  the  joint  between 
the  flanges.  Then,  when  the  crucibles  are  separated  some  mercury 
will  adhere  to  the  iron  crucible  and  be  lost.  If  it  chances  that  no  iron 
crucible  of  proper  dimensions  can  be  obtained  it  is  possible  to  use  a 
larger  one  by  setting  a  smaller  crucible  inside  of  the  larger  one. 
This  crucible  must  be  tall  enough  to  reach  a  little  above  the  level  of  the 
flanges.  The  iron  crucible  should  be  set  in  an  exactly  fitted  hole  in  a 
heavy  asbestos  board.  This  prevents  the  gold  crucible  from  getting 
too  hot.  The  gold  crucible  is  cooled  by  means  of  a  water  jacket  made 
of  a  large  piece  of  glass  tubing  fitted  to  the  crucible  by  means  of  a 
piece  of  thin-walled  rubber  tubing  such  as  that  used  with  Gooch 
crucibles.  The  glass  tube  is  fitted  with  a  two  hole  stopper  and  water 
circulated  through  it.  The  circulation  of  water  must  not  be  too  rapid 
as  the  gold  amalgamates  best  if  kept  between  50°  and  90°.  Another 
method  of  circulating  water  is  the  constant  level  siphon  device  used 
on  water  baths.  In  this  case  the  top  of  the  cooling  tube  is  left  open. 
Method  of  Analysis. 

The  organic  mercury  compound  is  weighed  in  the  iron  crucible 
(in  the  small  inner  one  if  two  are  used),  and  thoroughly  mixed  with 
five  times  its  weight  of  finely  powdered  anhydrous  sodium  carbonate. 
In  some  cases  powdered  barium  peroxide  must  be  added  to  insure  com- 
plete oxidation  .  This  is  not  usually  necessary.  The  mixture  is  covered 
with  a  thin  layer  of  anhydrous  sodium  carbonate  and  then  with  ten  to 
twenty  parts  of  dry  powdered  barium  carbonate.  In  cases  in  which 
an  unusually  large  amount  of  water  is  formed  a  layer  of  powdered 
barium  oxide  may  be  put  in  before  the  barium  carbonate  is  added. 

The  iron  crucible  is  now  fitted  to  the  gold  crucible,  the  rings  are 
put  in  place  and  the  flanges  of  the  two  crucibles  are  brought  tightly  to- 
gether by  means  of  the  four  screws.  The  bottom  of  the  iron  crucible 
is  put  through  the  hole  in  the  asbestos  board  and  the  cooling 
device  is  fitted  to  the  gold  crucible.  The  bottom  of  the  iron  crucible 


APPENDIX  A  367 

is  then  heated  very  gently.  Almost  all  failures  in  this  method  of  analy- 
sis are  due  to  too  rapid  or  too  high  heating.  The  heat  used  is  gradu- 
ally increased.  Thirty  minutes  heating  is  sufficient.  After  a  few  trials 
it  is  easy  to  adjust  the  heating  for  a  given  set  of  crucibles.  At  the  end 
of  the  heating  the  gold  crucible  is  disconnected.  The  flange  should 
be  examined  carefully  for  any  traces  of  amalgam.  If  any  are  de- 
tected there  has  probably  been  a  loss  of  mercury.  The  amalgam  is 
rinsed  carefully  with  alcohol  and  dried  in  a  vacuum  desiccator.  It  is 
then  weighed.  After  weighing,  the  mercury  is  removed  by  heating  the 
gold  crucible  gently  in  a  Bunsen  flame.  It  is  then  cooled  in  a  desicca- 
tor. It  is  then  ready  to  be  weighed  for  another  run.  A  complete  mer- 
cury analysis  may  be  run  by  this  process  in  two  and  a  half  hours. 
Close  supervision  is  needed  during  only  a  small  portion  of  this  time. 

Halogens  do  not  interfere  with  the  process  except  in  the  case  of 
some  iodomercuri  compounds.  In  the  case  of  some  of  these  compounds 
iodine  sublimes  on  the  amalgamated  gold  crucible  and  probably  re- 
acts with  the  mercury  to  some  extent.  The  escape  of  the  iodine  is 
prevented  by  a  layer  of  powdered  sodium  hydroxide  placed  under  the 
barium  carbonate  layer. 

A  determination  of  halogen  in  the  residue  may  be  made  by  trans- 
ferring it  quantitatively  to  a  suitable  vessel,  adding  nitric  acid,  and 
then  precipitating  by  silver  nitrate  solution  in  the  usual  way.  Of 
course,  the  materials  used  must  be  halogen  free. 


APPENDIX  B. 

Proprietary  Mercurials. 

AfridoL    The  sodium  salt  of  o'-hydroxymercuri-o-toluic  acid.1 
Anogon.    A  mixed  mercurous  and  mercuric  compound  of  diiodo- 

phenol  sulfonic  acid  ("Sozoiodol").     It  is  formulated  as  Hg  —  0  — 

C6H2I2  —  S03  —  Hgl.2    It  is  also  called  Meriodin. 

Aspirochyl.    Mercuric  salt  of  atoxyl  (p-arsanilic  acid)  .3 

Asterol.     Mixture  of  ammonium  tartrate  with  the  mercuric  salt 

of  p-phenol  sulfonic  acid.4 

Asurol.     A  water  soluble  compound  of  anhydro  mercurisalicylic 

acid  and  the  sodium  salt  of  a-hydroxy-(3-aminoisobutyric  acid.5     It 

probably  has  the  formula, 

CO,Na 

—  OH  CH3 

/ 

—  HgO  —  CO  —  C  —  CH2NH2. 

\ 
OH 

Asyphil.    Mercuric  salt  of  atoxyl.    Same  as  Aspirochyl.6 
Atoxiphil.    A  mercury  compound  derived  from  the  anilide  of  meta- 

arsenic  acid,  C6H5NH  —  As02. 7 

Contraluesin.    It  contains  arsenic  and  mercury  in  combination  or 

mixture  with  sozoiodol,  quinine,  and  salicylic  acid.8 

1  Biochem.  Z.  33  (1911),  399.     Chem.  Zentr.  1911  I  695,  II  1877. 

2  D.  R.  P.  245,534.     Frankel,  674. 

•  Chem.  Zentr.  1909  II  739,  1817. 

•  Frankel,  674. 

*Therap.  Monatsh.  23  (1909),  4.  Chem.  Zentr.  1910  I  948.  Biochem.  Z.  32  (1911), 
509;  33  (1911),  387;  57  (1913),  260.  Frankel,  664.  Note. — Frankel  makes  the  state- 
ment that  asurol  is  the  sodium  compound  of  hydroxymercurichlorophenoxyacetic  acid. 
This  is  apparently  an  error. 

•  Ohem.  Zentr.  1908  II  1891. 

7  Chem.  Zentr.  1908  II  1898. 

8  Munch,  med.  Wochenschr.  60,  62.     Ohem.  Abst.  7   (1913),  863.     Biochem.  Z.  65 
(1914),  468. 

368 


APPENDIX  B  369 

Embarin.    Anhydride  of  hydroxymercuri  sulfosalicylic  acid, 

C02H 

-OH     . 
H03S—  I II  —  HgOH 

The  preparation  appears  as  a  liquid  containing  one-half  of  one  per 
cent  of  acoin.9 

Enesol.  This  substance  is  variously  described:  (1)  A  mechanical 
mixture  of  anhydro  mercurisalicylic  acid  and  arrhenal,  CH3  —  AsO 
(ONa)2.  (2)  An  "acid  salicyl  ester  of  arsenic  acid  in  which  the  three 
hydroxyl  groups  are  replaced  by  mercury."  (3)  The  mercuric  salt  of 
3-carboxy-4-hydroxyphenyl  arsonic  acid.10 

Hermophenyl.    Mercury  sodium  salt  of  phenol  disulfonic  acid.11 

Hydrargyroseptol.  "Quinosol-mercury"  and  sodium  chloride, 
«C9H6NO  —  S03Hg.2NaCL" 12 

Hydrargyrol.  Mercuric  salt  of  p-phenol  sulfonic  acid.  It  is  used 
in  "Asterol." 18 

Hydryl.  The  product  from  the  action  of  mercuric  oxide  on  the 
monoso'dium  salt  of  3-methyl-4-acetaminophenyl  arsonic  acid  (Orsu- 
dan)  is  formulated  as  a  salt  of  N-Mercuribis-  (3-methyl-4-amino-5,  6- 
dihydroxymercuriphenyl  arsonic  acid) . 14 

Levurargyre.  A  mercury  compound  prepared  from  nucleic  acid 
from  beer  yeast.15 

Levuretin.  A  mercury  preparation  with  "completely  masked"  mer- 
cury.16 

Meracetin.  Anhydro  mercuripyrocatechinacetic  acid.  It  is  prob- 
ably the  anhydride  or  inner  salt  of  3-hydroxymercuri-2-hydroxyphe- 
noxyacetic  acid.17 

Mergal.     Mercuric  cholate,  Hg(C24H3905)2. 18 

9  Biochem.  Z.  57  (1913),  267.     Frankel,  663,  666. 

™Ber.  41  (1908),  933.  Biochem.  Z.  57  (1913),  260.  Chem.  Alst.  10  (1916),  951. 
Frankel,  663.  Realenzyk.  Pharm.  VI  562.  Morgan,  "Organic  Compounds  of  Arsenic 
and  Antimony,"  1918,  p.  198. 

11  Biochem.  Z.  32  (1911),  59. 

12  Realenzyk.  Pharm.  VI.  457. 

13  Thorpe,  Dictionary  of  Applied  Chem.  Ill  454. 
"Morgan,  184. 

18  Realenzyk.  Pharm.  VIII  183. 

18  lUd. 

"Frankel,  664. 

18  Merck's  Index,  1907,  p.  283.     Frankel,  667. 


370  COMPOUNDS  OF  MERCURY 

Mercurochrome-220.     Hydroxymercuridibromofluorescein.19 

Mercurol.    A  mercury  nucleinate.20 

Mercurophen.  Sodium  compound  p-hydroxymercuri-o-nitro- 
phenol.21  It  is  also  known  as  "No.  99." 

Merlusan.    A  mercury  tyrosin  compound.22 

Novasurol.  A  combination  of  the  sodium  salt  of  hydroxymercuri- 
chlorophenoxyacetic  acid  and  diethyl  barbituric  acid.23 

Phenegole.  (Egole.)  Mercuric  salt  of  o-nitrophenol-p-sulfonic 
acid.24 

Providol.    Sodium  compound  of  o,  p-dihydroxymercuriphenol.25 

Sublamin.  A  double  compound  of  mercuric  sulfate  and  ethylene 
diamine.26 

Toxynon.    Sodium  salt  of  hydroxymercuriacetaminobenzoic  acid.27 

Upsalan.    Sodium  compound  of  p-hydroxymercuri-o-chlorophenol.28 

18  J.  Am.  Chem.  Soc.  42  (1920),  2359.    J.  Am.  Med.  Assn.  73  (1919),  1483. 

20  Realenzyk.  PJiarm.  VIII  619. 

21  Frankel,  665. 

22  Ibid.,   661. 

23  Ibid.,  664. 
^Realcnzyk.  Pliarm.  IV  504. 

26  Frankel,  659. 

"Gazz.  chim.  ital.  39  I   (1909),  143. 

27  Biochem.  Z.   57    (1913),  260.     Frankel,  664.     Note. — This  substance  is  given   a 
formula  in  which  the  carboxyl  and  acetHmino  groups  are  in  the  meta   position.     It  is 
thus  2-hydroxymercuri-5-acetaminobenzoic  acid.     As  a  substance  of  this  structure  would 
be  rather  difficult  to  make  it  is  possible  that  it  may  be  a  derivative  of  p-aminobenzoic 
acid  instead  of  the  meta  acid. 

28  Frankel,  659. 


APPENDIX  C. 

Bibliography  of  Biological  and  Pharmacological  Work  with  Organic 
Mercury  Compounds. 

References  to  Medical  Journals. 


Am.  J.  Syphilis  1  (1917),  1  ff. 

AePP   13   (1880),  86;   22   (1887),  253; 

23    (1887),    91;    32    (1893),   456;    51 

(1903),  248;  68  (1912),  318. 
Arch.    Path.'  Anat.    33     (1865?),    71. 

Kiihne  &  Rudueff. 
Arch.  Physiol.  56  p.  349. 
Beitr.  chem.  Physiol.  &  Path.  6  (1905), 

296 

Ber.  Wien.  Akad.  II  60  (1870),  283. 
Bed.  klin.  Wochschr.  (1899),  229. 
Chem.  Zentr.  1910  II  1764. 
Derm.  Wochschr.  (1912),  566. 
Derm.  Zeitschr.  13  (1906),  827. 
Deut.  med.  Wochschr.  38  (1912),  543; 

38    (1912),    1582,    1822;    39    (1913), 

1409;  41  (1914),  74. 
Deut.  med.  Ztg.  (1893),  77. 
J.  Am.  Med.  Assn.  68  (1911),  1458;  66 
(1916),  1019;  73  (1919),  1483. 


/.  Cutaneous  Diseases  33   (1915),  No. 

12. 

J.  Urol  2  (1918),  107;  3  (1919),  1. 
Med.    Klin.    (1908),    Heft    44;     (1910) 

1405;    (1911),   Blumenthal?;    (1912), 

1557;  (1912),  No.  29. 
Med.  Record  89  (1916),  58. 
Munch,  med.  Wochschr.  44  (1897),  81; 

(1913),   No.  2;   57    (1910),  2079;   62 

(1916),  1638. 

"Systems  Mat.  Medicin"  1  102. 
Therap.  Monatsh.   (1890),  51,   128;   23 

(1909),  4. 
Veroff.  aus  d.  Gebiete  d.  Militdrsani- 

tdtswes.  38  (1907),  20. 
Wien.  Anzeiger  (1873),  14. 
Z.  Hyg.  Infekt-Krankh.  25  (1897),  1  ff; 

66    (1911),   497;    70    (1912),   24;    77 

(1915),  436;  82  (1916),  279. 
Zentr.  klin.  Med.  14  (1893),  49. 


References  to  Pharmaceutical  Journals. 


Apoth.  Ztg.  (1909),  98,  661;  (1911), 
913;  (1912),  377;  (1913),  431,  630, 
824,  887. 

Arch.  Pharm.  (2)  117  (1871),  218;  (2) 
147  (1871),  218;  (2)  148  (1871),  201; 
198  (1871),  205;  (1885),  918;  (3)  227 
(1889),  172,  961;  228  (1890),  9,  77; 
232  (1894),  329;  236  (1898),  374,  622; 
238  (1900),  41;  239  (1901),  114;  242 
(1904),  682;  243  (1905),  1,  617;  244 
(1906),  120;  245  (1907),  25;  250 
(1912),  62;  252  (1914),  449;  253 
(1915),  274;  254  (1916),  498;  255 
(1917),  191;  256  (1918),  263. 

Arch,  jarmacol.  sperim.  11   (1911),  457. 

Brit.  Arch.  (2)  27  (1838),  217;  28 
(1838),  38. 


Ber.  pharm.  Ges.  6  (1896),  285;  20 
(1910),  201;  29  (1919),  156. 

Bull.  sci.  pharm.  18  (1913),  639. 

Chem.  Druggist  78  (1911),  20. 

Fortschritte  d.  Pharmazie  14  (1914), 
303. 

Jahresb.  prakt.  Pharm.  6  (1832),  250. 

J.  pharm.  3  (1816),  509;  17  (1829),  356. 

/.  pharm.  chim.  (3)  13  (1848),  245; 
(4)  8  (1868),  265;  (4)  10  (1869),  96, 
251;  (5)  6  (1882),  169;  (5)  18  (1888), 
257,  296;  (5)  21  (1890),  465;  (5)  28 
(1893),  196;  (5)  29  (1894),  227;  (6) 
2  (1895),  289;  (6)  9  (1899),  7,  371; 
(6)  11  (1900),  165;  (6)  12  (1900), 
150;  (6)  14  (1901),  356;  (6)  16 
(1902),  5,  297;  (6)  21  (1905),  388; 


371 


372 


COMPOUNDS  OF  MERCURY 


(6)  22  (1905),  107,  247;  (6)  24  (1906), 
21;  (6)  25  (1907),  423;  (6)  26  (1907), 
300;  (6)  30  (1909),  145;  (7)  6  (1912), 
433;  (7)  11  (1915),  279;  (7)  15 
(1917),  33,  241. 

J.  Pharm.  d'Anvers  58,  p.  98. 

J.  Pharm.  Liege  3  Article  2. 

Mag.  Pharm.  24  (1828),  138. 

Nederl.  Tijdschr.  Pharm.  8  (1896),  117. 

Neues  Jahresb.  Pharm.  36   (1872),  19. 

Pharm.  Zentralhalle  31  (1890),  239;  37 
(1897),  606;  46  (1905),  385,  479,  644, 
846,  935;  47  (1906),  347,  555,  623,  727, 
1028;  48  (1907),  44,  336;  55  (1914), 
91,  121,  126,  169,  217. 


Pharm.  J.  (3)  3  (1874),  442,  772;  (3) 
16  (1886),  762;  (3)  19  (1889),  841; 
(3)  21  (1890),  253;  (4)  37  (1913),  144. 

Pharm.  Weekblad  43  (1906),  1105. 

Pharm.  Ztg.  46  (1901),  352,  915;  54 
(1909),  17,  310,  989,  1026;  55  (1910), 
284,  558,  725;  56  (1911),  34,  75,  558, 
605,  636,  738,  903;  57  (1912),  1031; 
60  (1916),  724. 

Neues  Repert.  Pharm.  17  (1868),  257; 
22  (1873),  65. 

Report.  Pharm.  4  (1898),  28. 

Schweiz.  Woch.  Pharm.  47  (1909),  177. 

Z.  Pharm.  (1851),  2. 


See  also  references  to  Biochemische  Zeitschrift  and  Zeitschrift  jur 
physiologische  Chemie  in  Appendix  D,  "Miscellaneous  References." 


APPENDIX  D. 

Supplementary  Bibliographical  Lists. 


Mercury-Nitrogen  Compounds. 

The  only  organic  compounds  containing  the  Hg  —  N  linkage  which 
have  been  carefully  studied  are  the  mercury  compounds  of  the  acid 
amides  and  imides.  These  substances  dissolve  mercuric  oxide  readily 
giving  N  —  Hg  compounds.  These  substances  behave  like  mercuric 
salts  except  that  they  do  not  react  readily  with  bases.  Sulfides  give 
mercuric  sulfide.  Inorganic  halides  break  the  N  —  Hg  linkage  accord- 
ing to  the  equation 

>  N  —  Hg  —  N  <  +  2NaX  +  2H20  -»  2  >  NH  +  2NaOH  +  HgX2. 

Sodium  thiosulfate  produces  a  similar  change.     Acids  give  mercuric 
salts  and  the  original  amide  or  imide. 


Mercury  acetamide. 
Ann.  103  (1857),  324. 
Ann.  chim.  phys.  (3)  52  (1858),  506. 
Ber.  7  (1874),  624;  23  (1890),  1553; 

26  (1893),  423,  987. 
Chem.  News.  78  (1898),  250. 
/.  Chem.  Soc.  73  (1898),  791. 
Ber.  32  (1899),  1358. 
Z.  physik.  Chem.  28  (1899),  392;  42 

(1903),  690. 

Monatsh.  23  (1902),  1147. 
/.  Am.  Chem.  Soc.  28  (1906),  1025. 

Miscellaneous  N-Hg  compounds. 

Am.  Chem.  J.  18  (1896),  542. 

Ann.  130  (1864),  203. 

Chem.  Abst.  5  (1911),  3880. 

Chem.  Zentr.  1895  II  226;  1913  II 
324. 

Compt.  rend.  112  (1891),  997. 

Ber.  5  (1872),  382;  7  (1874),  624;  17 
(1884),  133;  23  (1890),  1553;  26 
(1893),  985;  33  (1900),  2228;  35 
(1902),  1310,  2721;  45  (1912),  1731. 


Biochem.  Z.  33  (1911),  381. 

Bull.  soc.  chim.   (3)   11   (1894),  573; 

(3)  15  (1896),  863. 
Gazz.  chim.  ital.  27  I  (1897),  567;  28 

II    (1898),   122,  434;   39  I    (1909), 

143. 

J.  Chem.  Soc.  91  1907),  1045. 
J  prakt.  Chem.  (2)  21  (1880),  18. 
Merck's  Index  1907,  pp.  278,  281. 
"Realenzyk.  Pharm."  VI  486. 
Z.  anorg.  Chem.  15  (1897),  208. 
Z.  Chem.  (2)  4  (1868),  303. 
Z.  physik.  Chem.  11  (1893),  466;  28 

(1899),  385;  42  (1903),  690. 

Sulfur-Mercury  Compounds. 

Ann.  11  (1834),  3,  17;  51  (1844),  303; 
72  (1850),  19;  119  (1861),  146;  120 
(1861),  64;  136  (1865),  77;  140 
(1866),  87;  146  (1868),  148;  154 
(1870),  122,  179;  241  (1887),  117; 
267  (1892),  173;  359  (1908),  202; 
371  (1909),  201. 

Ann.  Spl.  4  (1865),  97. 


373 


374 


COMPOUNDS  OF  MERCURY 


Ber.  I  (1868),  172;  2  (1869),  544;  7. 

(1874),    648;    15    (1882),    125;    48 

(1915),  1427;  53   (1920),  568,  1670, 

1737. 
Bull.  soc.  chim.   (4)    9   (1911),  532; 

(4)  17  (1915),  353. 
Ghent.  Zentr.  1908  I  1491. 
Compt.  rend.  70  (1870),  626. 
J.  prakt.  Chem.  (1)  53   (1851),  380; 


(2)  15  (1877),  205;   (2)  84  (1911), 

750. 

Monatsh.  10  (1889),  883. 
J.  Chem.  Soc.  95   (1909),   1918;    1Q1 

(1912),  935. 

Z.  anal.  Chem.  34  (1895),  457. 
Z.  anorg.   Chem.  6    (1894),  248;    14 

(1897),  295;  17  (1898),  29. 
Z.  physik.  Chem.  11  (1893),  466. 


Bibliography  of  Double  Compounds  of  Mercuric  Salts  with  Organic 

Substances. 


Methyl  alcohol.     Z.  anorg.  Chem.  53 

(1907),  327. 
Glycerol.     J.     prakt.     Chem.     (2)     55 

(1897),  83. 

Organic  sulfur  compounds. 
Ann.  51  (1844),  303. 
Ann.  87  (1853),  369. 
Ann.  107  (1858),  234. 
Compt.  rend.  36  (1853),  1095. 
Compt.  rend.  46  (1858),  1280. 
Ann.  126  (1863),  279. 
J.  prakt.  Chem.  (2)  14  (1876),  199. 
Ann.  243  (1888),  204;  272  (1893),  276. 
Z.  physiol.  Chem.  20  (1895),  269. 
Z.  anorg.  Chem.  15  (1897),  14. 
Ber.  31  (1898),  2283. 
J.    Chem.   Soc.   77    (1900),    160;    91 

(1907),  1394. 

J.  prakt.  Chem.  (2)  66  (1902),  423. 
J.  Chem.  Soc.  101    (1912),  936;    103 

(1913),  3. 
Aliphatic  amines. 

Ann.  83  (1852),  349;  199  (1875),  321. 
Ber.  1  (1868),  171;  12  (1879),  2323. 
J.  prakt.  Chem.  (2)  39  (1889),  99. 
Ber.  31   (1898),  2283;  38  (1905),  975. 
Ann.  305  (1899),  191. 
J.  Am.  Chem.  Soc.  34  (1912),  292. 
Unsaturated  amines. 

Ann.  134  (1865),  11. 
Quarternary  ammonium  salts. 
Ann.  78  (1851),  272;  107  (1858),  223; 

108  (1858),  6. 
Ber.  16  (1883),  2737;  31  (1898),  2283; 

38  (1905),  2686. 

J.  Chem.  Soc.  109  (1916),  1299. 
Aliphatic  diamines. 

Frankel,  "Arzneimittelsynthese."  4th 

Ed.,  1919,  p.  670. 
"Realenzyk.  Pharm."  VI  481. 
Ber.  18  (1885),  1925;  19  (1886),  2585; 

20  (1887),  1445,  2217. 
J.  prakt.  Chem.   (2)   47   (1893),  444, 

512. 


Z.  physiol.  Chem.  20  (1895),  288,  291. 

J.  Chem.  Soc.  101  (1895),  1552. 

J.  prakt.  Chem.  (2)  55  (1897),  91. 

Ber.  39  (1906),  3593. 
Urea. 

J.  prakt.  Chem.  (!)  35  (1845),  51. 

Compt.  rend.  21  (1845),  636. 

Ann.  62  (1847),  78;  83  (1852),  339; 
82  (1852),  311;  101  (1857),  321. 

Jahresber.  1857,  364. 

J.  prakt.  Chem.  (2)  47  (1893),  567. 

Z.  Chem.  (2)  4  (1868),  303. 

J.  Chem.  Soc.  22  (1869),  12. 

Ann.  150  (1869),  238. 

J.  prakt.  Chem.  (2)  30  (1884),  92. 

Ber.  18  (1885),  461. 

Ann.  chim.  phys.  (6)  9  (1886),  300. 

J.  prakt.  Chem.  (2)  47  (1893),  567. 

J.  Chem.  Soc.  63  (1893),  199. 

Gazz.  chim.  ital.  27  I  (1897),  1. 

Z.  anal.  Chem.  39  (1900),  551. 

Ber.  36  (1903),  1156. 

Z.  anorg.  Chem.  49  (1906),  14. 

Am.  Chem.  J.  47  (1912),  396. 
Cyanides. 

Ann.  110  (1859),  202;  154  (1870),  121. 

J.  prakt.  Chem.  (2)  4  (1871),  38;  (2) 
6  (1872),  98. 

Ber.  16  (1883),  2737. 

J.   Chem.   Soc.   77    (1900),   163;    109 

(1916),  1299. 
Amino  acids. 

Ann.  62  (1847),  301;  80  (1851),  123; 
82  (1852),  232;  85  (1853),  289;  101 
(1857),  321;  119  (1861),  43. 

J.  prakt.  Chem.  (2)  3  (1871),  311; 
(2)  11  (1875),  317;  (2)  20  (1879), 
334. 

Compt.  rend.  78  (1874),  1707. 

Z.  anal.  Chem.  22  (1883),  341. 
Nitrotoluenes. 

Gazz.  chim.  ital.  36  I  (1906),  229. 
Aromatic  mercury  compounds. 

Gazz.  chim.  ital.  32  II  (1902),  277. 


APPENDIX  D 


375 


Ann.  406  (1914),  250. 
Friinkel,     "Arzneimittelsynthese,"     4th 
Ed.,  1919,  pp.  663,  670. 

D.  R.  P.  261,  875;  264,  267;  247,  625. 
Diphenyl    iodonium    chloride    and   re- 
lated substances. 

Ber.  31  (1898),  915. 

Gazz.  chim.  ital.  36  I  (1906),  229. 
Aromatic  amines. 

J.  prakt.  Chem.  (1)  36  (1845),  97. 

J.  Chem.  Soc.  7  (1855),  75. 

Ber.  16  (1883),  2737. 

Ann.  224  (1884),  349. 

J.  Chem.  Soc.  53  (1888),  555. 

Ber.  21  (1888),  856,  1792. 

J.  prakt.  Chem.  (2)  39  (1889),  100. 

Monatsh.  10  (1889),  899. 

Ann.  260  (1890),  6. 

Gazz.  chim.  ital.  23  II  (1893),  525. 

Z.  anorg.  Chem.  15  (1897),  208. 

J.  Chem.  Soc.  101  (1895),  1556. 

Ber.  31  (1898),  2293. 

J.  Chem.  Soc.  79  (1901),  839. 

Z.  anorg.  Chem.  46  (1905),  390;  57 
(1908),  98. 

Ann.  365  (1909),  50. 

Gazz.  chim.  ital.  39  I  (1909),  149. 
Benzpnitrile.  * 

Ber.  47  (1914),  1369. 
Pyrrole. 

Ann.  105  (1858),  356. 
Piperidine. 

J.  prakt.  Chem.  (2)  39  (1889),  99; 
(2)  43  (1891),  159;  (2)  47  (1893), 
475;  (2)  49  (1894),  401. 

Compt.  rend.  115  (1892),  880. 

Gazz.  chim.  ital.  27  I  (1897),  19. 

Z.  anorg.  Chem.  15  (1897),  230. 

J.  Chem.  Soc.  103  (1913),  6. 
Alkyl  piperidines. 

Ber.  18  (1885),  912;  33  (1900),  3515. 

J.  Chem.  Soc.  103  (1913),  6. 
Pyridine. 

Ber.  21  (1888),  1587. 

Ann.  247  (1888),  5  ff. 

Monatsh.  10  (1889),  892. 

Compt.  rend.  112  (1891). 

Gazz.  chim.  ital.  25  II  (1895),  423. 

Z.  anorg.  Chem.  15  (1897),  228. 

Ber.  37  (1904),  1260,  4610;  38  (1905), 
975,  2003. 

Z.  anorg.  Chem.  46  (1905),  367;  44 
(1905),  8;  57  (1908),  101. 

Chem.  Zentr.  1910  II  1741. 

/.  Chem.  Soc.  103  (1913),  6. 
Dipyridyl. 

J.  Chem.  Soc.  22  (1869),  409. 

Ber.  31  U898),  2282. 

J.  prakt.  Chem.  (2)  84  (1911),  203. 


Methylpyridines. 

Ann.  60  (1846),  99. 

Ber.  18  (1885),  51,  3092,  3437. 

Bull.  soc.  chim.  (2)  43  (1885),  172. 

Ber.  20  (1887),  812,  1660,  2732. 

Ann.  247  (1888),  13. 

Ber.  21  (1888),  293. 

Gazz.  chim.  ital.  27  I  (1897),  23. 

Z.  anorg.  Chem.  15  (1897),  229. 

J.   Chem.  Soc.   81    (1902),  452;    103 

(1913),  3. 
Dimethylpyridines. 

Ann.  80  (1851),  61;  231  (1885),  22. 

Ber.  18  (1885),  51,  914,  3441;  20 
(1887),  129. 

Ann.  247  (1888),  30. 

Ber.  21  (1888),  1008;  29  (1896),  2997; 
32  (1899),  2528;  34  (1902),  3700. 

J.  Chem.  Soc.  81  (1902),  452. 

Chem.  Z.  2  (1903),  414;  Chem.  Zentr. 

1903  I  1034. 
Ethylpyridines. 

J.  prakt.  Chem.  (2)  43  (1891),  155. 

Ann.  301  (1898),  152. 

Ber.  31  (1898),  290. 
Methylethylpyridines. 

Ber.  3  (1870),  262;  24  (1892),  3486. 
Trimethylpyridines. 

Ber.  21  (1888),  1012,  2714;  25  (1892), 
3487;  29  (1896),  2998. 

/.  Chem.  Soc.  81  (1902),  455. 
Diethylpyridine. 

Ann.  247  (1888),  49. 
Propylpyridine . 

Ann.  247  (1888),  24. 
Allylpyridine. 

Ibid.  28. 
Quinoline. 

Ann.  42  (1842),  312;  44  (1842),  279. 

Ann.  chim.  phys.  (3)  9  (1843),  173. 

Ann.  47  (1843),  83;  52  (1844),  139. 

Compt.  rend.  57  (1863),  837. 

Ann.  131  (1864),  114;  247  (1888), 
94. 

Monatsh.  10  (1889),  892. 

Ber.  23  (1890),  438. 

Gazz.  chim.  ital.  25  I  (1895),  399  ff. 

Ann.  301  (1898),  133. 

Z.  anorg.  Chem.  46  (1905),  365. 

Chem.  Zentr.  1910  II  1743. 

J.  prakt.  Chem.  (2)  84  (1911),  206. 
Miscellaneous  nitrogen  compounds. 

Ann.  47  (1843),  64;  52  (1844),  13; 
175  (1875),  43;  208  (1881),  137;  263 
(1891),  274. 

Ber.  15  (1882),  2106. 

Chem.  Zentr.  1913  II  1182. 
Aromatic  ketones,  thienyl  ketones. 

Ann.  267  (1892),  172. 


376 


COMPOUNDS  OF  MERCURY 


Alkaloids. 
"Gmelin  -  Kraut  -  Friedheim  -  Peters 

Handbuch  V,"  part  II,  554. 
Ann.  41  (1842),  118;  42  (1842),  315; 

66  (1848),  268;  70  (1849),  73. 
J.  Chem.  Soc.  1  (1849),  345. 
Ann.  73  (1850),  372,  211;  74  (1850), 

201;  77  (1851),  208. 
Phil.  Mag.  (3)  37  (1851),  481. 
Ann.  82  (1852),  311;  83  (1852),  339; 

87  (1853),  8. 

J.  prakt.  Chem.  (1)  60  (1853),  239. 
Jahresber.    1872,    p.    270;     1873,    p. 

962. 

Ber.  16  (1883),  2740. 
Aromatic  sulfur  compounds. 
Ann.  243  (1888),  204. 
Ber.    24     (1891),    757;     31     (1898), 

2287. 
J.   Chem.   Soc.   77    (1900),    164;    81 

(1902),  1556;  91  (1907),  1395. 
Ber.  47  (1914),  277. 


Aromatic  tellurides. 

Ber.  47  (1914),  278. 
Miscellaneous. 

Ann.  229  (1885),  305;  233  (1886),  49. 

Ber.  19  (1886),  700. 

J.  Chem.  Soc.  49  (1886),  246. 

J.  prakt.  Chem.   (2)  39   (1889),  102; 
(2)  39  (1889),  99  ff. 

Monatsh.  10  (1889),  891. 

Compt.  rend.  112  (1891),  995. 

J.  prakt.  Chem.  (2)  43  (1891),  155. 

Ann.  267  (1892),  172. 

J.  prakt.  Chem.  (2)  47  (1893),  566. 

Ber.  30  (1897),  2844. 

Gazz.  chim.  ital.  28  II  (1898),  113. 

J.  prakt.  Chem.  (2)  66  (1902),  423  ff. 

J.  Chem.  Soc.  81  (1902),  1560. 

Ber.  37  (1904),  3284. 

Chem.  Zentr.  1907  I  1103. 

J.  Am.  Chem.  Soc.  35  (1913),  951. 

Gazz.  chim.  ital.  43  II  (1913),  463. 

Chem.  Zentr.  1914  II  1195. 


Recent  Work  on  Acetylene  and  Mercuric  Compounds. 


1918. 

Chem.  Abst.  12   (1918),  42.     Fr.  Pat. 

Addition  20,202  to  479,656. 
Ibid.  280.    U.  S.  Pat.  1,247,270. 
Ibid.  484.    Swed.  Pat.  43,001. 
Ibid.  588.    Can.   Pat.    181,655,    181,656, 

181,657. 

Ibid.  1050.    Brit.  Pat.  112,765,  112,766. 
Ibid.  1558.     Norw.  Pat.  28,538. 
Ibid.  1885.    Brit.  Pat.  115,899. 
Ibid.  2326.     Dan.  Pat.  23,175. 

1919 
Chem.  Abst.  13  (1919),  1595.    Brit.  Pat. 

124,194. 
Ibid Brit.  Pat.  124,702. 


Ibid.  2040.  U.  S.  Pat.  1,304,989. 

Ibid.  2219.  U.  S.  Pat.  1,306,964. 

Ibid.  2374.  Swiss  Pat.  78;339,  78,947. 

Ibid U.      S.      Pat.      1,310,743, 

1,310,984. 


Chem.  Abst.  14  (1920),  72.    U.  S.  Pat. 

1,319,365.  Brit.  Pat.  130,138,  130,650, 

131,084. 

Ibid.    284.  Brit,  Pat.  132,529. 

Ibid.    288.  Brit.  Pat.  132,557,  132,559. 

Ibid.  2040.  U.  S.  Pat.  1,304,989. 

Ibid.  2203.  Brit.  Pat.  140,784. 

Ibid.  2344.  U.  S.  Pat.  1,343,715. 

Ibid.  3427.  U.  S.  Pat.  1,351,990. 


Miscellaneous  References. 


Ann.  154  (1870),  252;  419  (1919),  266. 
Ann.  chimica  (4)  9  (1889),  258;  (4)  10, 

176;  (1898),  16. 
Ann.  chim.  phys.   (2)   39   (1828),  197; 

(7)  8  (1896),  268;  (8)  14  (1908),  311. 
Ann.  farmacoterap.  (1898),  16. 
Am.  Akad.  Krakau  (A)  (1910),  382. 
Arch.  Sci.  Phys.  Nat.  Geneve  6  (1898), 

385. 

Arch,  jarmacol.  7  (1908),  94. 
Arch.  farm,  sperim.  11  (1911),  457. 
Arch.  Physiol.  40  (1888),  533. 
Atti  accad.   Lincei   (5)    1    (1892),  312, 

431;  (5)  2  I  (1893),  423;  (5)  5  (1896), 


120;  (5)  8  I  (1899),  130;  (5)  9  I 
(1900),  255;  (5)  10  I  (1901),  362,  413; 
(5)  11  II  (1902),  65;  (1903),  294;  (5) 
14  II  (1905),  199;  (5)  15  II  (1906), 
459;  (5)  16  I  (1907),  87;  (5)  21  II 
(1912),  88,  640,  773. 

Ber.  6  (1873),  440;  15  (1882),  830. 

Ber.  Berl.  Akad.  (1866),  586. 

Ber.  Wien.  Akad.  9  (1852),  252;  (II)  86 
(1882),  1158;  (II)  99  (1890),  173. 

Biochem.  Z.  11  (1908),  294;  24  (1910), 
173,423;  25  (1910),  341;  32  (1911),  59, 
511;  33  (1911),  381;  35  (1911),  505; 
36  (1911),  201;  37  (1911),  142;  39 


APPENDIX  D 


377 


(1912),  50;  40  (1912),  498;  57  (1913), 
260;  65  (1914),  460. 

Boll.  chim.  farm.  39  (1901),  797;  40 
(1901),  791;  42  (1903),  577;  47  (1908), 
291,  567;  51  (1912),  397;  53  (1914), 
193;  56  (1917),  564. 

Boll.  soc.  med.  chim.  July,  1908. 

Bull,  acad.  Belg.  (3)  33  (1897),  821; 
(1903),  441. 

Bull.  soc.  chim.  (2)  14  (1870),  217. 

Chem.  Zentr.  1902  I  500;  1907  I  483; 
1915  II  565,  569,  1260. 

Chem.  Abst.  6  (1912),  2262. 

Chem.  News.  19  (1869),  28. 

Clin.  med.  Hal.  (1909),  339. 

Compt.  rend.  82  (1876),  1504;  112 
(1891),  340,  995;  117  (1893),  44,  284, 
518;  119  (1894),  559;  120  (1895),  628, 
781,  850;  121  (1896),  253;  126  (1898), 
1043,  1145,  1277,  1868;  127  (1898), 
963;  128  (1898),  429;  129  (1899),  113, 
379,  918;  130  (1900),  837,  1256,  1478, 
1511;  131  (1900),  346;  132  (1901), 
145,  635;  137  (1903),  255,  714;  140 
(1905),  1698,  1703;  142  (1906),  1200; 
144  (1907),  326,  1177;  146  (1908),  754; 
152  (1910),  1867;  153  (1911),  304, 
1520. 

Compt.  rend.  soc.  biol.  69  (1910),  508; 
74  (1913),  18. 

Edinburgh  Phil.  Trans.  20  II  (Ander- 
son). 

Gazz.  chim.  ital.  7  (1877),  421;  19 
(1889),  509;  20  (1890),  485;  21  II 
(1891),  294,  569;  22  I  (1892),  373;  22 
II  (1892),  32, -557,  563,  608;  23  II 
(1893),  521;  24  II  (1894),  449;  25  I 
(1895),  394;  25  II  (1895),  423;  26  I 
(1896),  54,  275;  29  I  (1899),  395. 

Giorn.  farm.  chim.  62  (1914),  489. 

/.  Physiol.  34  (1906),  84;  42  (1911), 
444. 

J.  prakt.  Chem.  86  (1862),  298;  (2)  13 
(1876),  437;  (2)  55  (1897),  88. 

L'Orosi,  12  (1889),  181;  13  (1890),  255; 
22  (1900),  369. 

Phil.  Mag.  (3)  13  (1838),  431;  Aug. 
1847;  (4)  20,  111;  (5)  2  (1876),  277. 

Phil.  Trans.  (1822),  357. 


Pogg.  Ann.  11  (1827),  64;  13  (1828), 
261;  28  (1823),  132;  31  (1834),  369; 
33  (1834),  80;  40  (1836),  62;  47 
(1839),  609;  93  (1855),  461;  106 
(1859),  500;  110  (1860),  142. 

Proc.  Camb.  Phil.  Soc.  15  (1909),  94. 

Proc.  Chem.  Soc.  8  (1892),  110;  18 
(1902),  249;  21  (1905),  95,  119,  242, 
248;  23  (1907),  246;  24  (1908),  267. 

Proc.  Nat.  Acad.  Sci.  1  (1915),  195. 

Proc.  Physiol.  Soc.  May  18,  1912. 

Proc.  Roy.  Soc.  14  (1865),  19;  19 
(1871),  431,  440;  80  (1908),  1. 

Rec.  tray.  chim.  36  (1917),  289,  306. 

Riv.  chim.  med.  farm.  2  (1884),  195. 

Sachs.  Ber.  62  (1910),  57. 

Schweiggefs  Ann.  59  (1830),  105. 

Staz.  sperim.  agrar.  ital.  33  (1900),  274. 

Studies  in  Physiol.  Chem.,  Yale,  2 
(1888),  95. 

Trans.  Roy.  Soc.  Edinburgh  21  (1857), 
571. 

Z.  angew.  Chem.  (1896),  596;  (1897), 
14;  (1900),  707;  (1901),  1191;  22 
(1911),  1967;  24  (1912),  677;  26 
(1913),  627. 

Z.  Biol.  26  (1891),  324. 

Z.  Chem.  Ind.  Roll.  1  (1906),  353;  2 
(1907),  171;  11  (1912),  120;  12 
(1913),  71. 

Z.  Chemotherapie,  1  (1912),  21. 

Z.  Krystallog.  51  (1912),  138. 

Z.  ges.  Schiess-Sprengstoff.  6  (1911), 
4  ff. 

Z.  Hyg.  Infekt.  25  (1897),  1;  66  (1910), 
497;  70  (1911),  24;  82  (1916),  279. 

Z.  Immunitat.  (I)  1  (1908),  108;  (I) 
16  (1913),  224;  (I)  20  (1914),  378; 
41  (1915),  47. 

Z.  physiol.  Chem.  15  (1890),  1;  20 
(1895),  267,  288;  22  (1896),  520;  23 
(1897),  505;  36  (1902),  401;  43  (1904), 
350;  44  (1905),  503;  47  (1906),  173; 
55  (1908),  352;  57  (1908),  49;  78 
(1912),  333;  83  (1913),  249. 

Z.  Untersuch.  Nahr.  Genussmitteln  16 
(1908),  389;  21  (1911),  92. 

Z.  Zuckerei  62  (1912),  318. 

Zentr.  Physiol.  4  (1890),  189. 


APPENDIX  E. 

Patents  on  Organic  Mercury  Compounds. 

German  Patents. 

Abbreviations.     C.  =  Chemisches  Zentralblatt. 
C.  A.  =  Chemical  Abstracts. 

Fr.  =  Frankel,  Die  Arzneimittelsynthese.  4th  Ed.  1919. 
Frdl.  =  Friedlander,  Fortschritte  der  Teerfarbenfabrika- 

tion. 

G.  K.  F.  P.  =  Gmelin-Kraut-Friedheim-Peters,  Handbuch  der 
anorg.  Chemie,  Vol.  V,  Part  II. 


48,459.     Fr.  659.  213,371. 

104,904.    Fr.  674.    Frdl.  V  724. 
118,050.    G.  K.  F.  P.  516. 

121,656.     Fr.  674.    Frdl.  V  724.  216,267. 

125,095.    G.  K.  F.  P.  968. 

125,392.     G.  K.  F.  P.  459.  216,828. 

132,660.    Frdl.  VI  1102.  219,966. 

137,560.    C.  1911  I  695. 
143,448.     C.  1903  II  403.    Frdl.  VII  715.       219,967. 

Fr.  661.  221,483. 

143,726.     C.  1903  II  474.  Ber.31  (1898),      224,435. 

2154.     J.  prakt.  Chem.   (2) 

89    (1914),   136.     Frdl.  VII      224,491. 

716.     Fr.  .662.  224,864. 

148,794.     (1902),  Raupenstrauch. 
157,663.    Fr.  674.  224,980. 

171,485.    C.   1906  II   385.     Frdl.  VIII      225,711. 

1231.  227,391. 

182,217.     (1905),  Reissert. 
185,042.    G.  K.  F.  P.  454.    Frdl.  VIII      228,877. 

1312. 
186,881.     G.  K.  F.  P.  483.     Frdl.     IX      229,574. 

162.  229,781. 

189,480.    G.  K.  F.  P.  790.  231,092. 

193,219.     (1906),  Klein.  231,396. 

201,903      C.    1908   II    1307.     Frdl.    IX 

1071.  233,437. 

203,791.     (1906),  Schmitz.  234,054. 

207,275.    C.  1909  I  1129. 
208,634.    C.  190911520.    C.  A.  3  (1909),       234,851. 

2036.    Frdl.  IX  1065. 

378 


C.   A.    4    (1910),    495.      Frdl. 

IX     1067.        C.     1909     II 

1393. 
Fr.    674.      C.    1909    II    2104. 

Frdl.  IX  1070. 
C.  1910  I  217. 
C.    1910    I    1078.      Frdl.    IX 

1069. 
Ibid. 

Frdl.  IX  1067. 
Frdl.  X  1262.    C.  A.  5  (1911), 

155. 

Frdl.  X  1289. 
Frdl.  X  1263.  C.  A.  5  (1911), 

156 

Frdl.  X  1283. 

Ibid.  C.  A.  5  (1911),  1165. 
Fr.  662.  Frdl.  X  1263.  C.  A. 

5  (1911),  2154. 
C.  A.  5  (1911),  2307.  C.  1911 

I  102.  Frdl.  X  1279. 
C.  1911  I  275. 
C.  1911  I  276. 
C.  1911  I  682. 
C.  A.  5  (1911),  2701.  Frdl.  X 

1284. 

C.  1911  I  1266. 
Frdl.  X  1276.  C.  A.  5  (1911), 

2910.  Fr.  665. 
C.  1911  I  1769.  Frdl.  X  1272. 

Fr.  660. 


APPENDIX  E 


379 


234,914.    Fr.   665.     Frdl.   X   1269.     C.  261,875. 

1911  II  112. 

235,356.  C.  A.  5  (1911),  3129.  Frdl.  X  264,267. 

1285.  C.  1911  II  170.  264,388. 

236.893.  Frdl.  X  1287.  C.  1911  II  404.  264,578. 

237787.  Frdl.  X  1251.  C.  1911  II  920.  267,411. 

239^57.  C.  1911  II  1398.  267,412. 

242.571.  Fr.  668.  C.  1912  I  384.  270,253. 

242.572.  C.  A.  6  (1912),  2146;  7  (1913),  271,820. 

867.  G.  K.  F.  P.  483.  Frdl.  272,289. 

X  1275. 

245,534.  Fr.  674.  C.  1912  I  1521.  C.  A.  272,291. 

6  (1912),  2495.   Frdl.  X  272,607. 

1281.  272,687. 

245,571.  Fr.  667.  Frdl.  X  1270.  272,688. 

246,207.  Fr.  667.  Frdl.  X  1271.  275,171. 

247,625.  Fr.  668.  Frdl.  X  1273.  C.  275,932. 

1912  II  166.  279,199. 

248,291.  Fr.  662.  C.  A.  6  (1912),  2675.  279,957. 

C.  1912  II  211.  281,009. 

249,332.  Fr.  665.  Frdl.  XI  1103.  C.  282,376. 

1912  II  465.  282,377. 

249,715.  C.  A.  6  (1912),  3165.  Frdl.  282,987. 

XI  1109.  Fr.  670.  286,097. 
250,746.  Fr.  660.  Frdl.  XI  1104.  C. 

1912  II  1245.  286,414. 

251,332.  Fr.  670.  Frdl.  XI  1112.  286,977. 

255,030.  Frdl.  XI  1116.  C.  1913  I  287,246. 

353.  288,965. 

261.081.  Frdl.  XI  1118.  289,246. 

261.082.  Ibid.  1119.  290,210. 
261,229.  Ibid.  1105.  C.  1913  II  193.  Fr.  293,692. 

671.  300,513. 

261,460.  Fr.  673.  C.  1913  II  324.  Frdl.  300,561. 

XI  1102.  302,911. 


Fr.  670.  Frdl.  XI  1107.  C. 

1913  II  395. 

Fr.  670.  Frdl.  XI  1106. 

Fr.  668.  Frdl.  XI  1114. 

Frdl.  XI.  1120. 

Ibid.  1108. 

Ibid.  1109. 

? 

Ibid.  1099.  Fr.  667. 

Fr.  661.  Frdl.  XI  1121.  C. 

1914  I  1469. 

Fr.  670.  Frdl.  XI  1175. 

Fr.  671. 

Frdl.  XI  1101. 

Frdl.  XI  1101. 

C.  A.  8  (1914),  3380. 

Fr.  667.  C.  1914  II  367. 

Fr.  670.  C.  1914  II  1175. 

Fr.  661.  C.  1914  II  1334 

Fr.  670.  C.  1915  I  73. 

Fr.  676. 

Fr.  676. 

Frdl.  XI  1912-14. 

C.  A.  10  (1916),  1080.  C.  1915 

II  569. 

C.  1915  II  565. 
C.  A.  10  (1916),  1694. 
C.  A.  10  (1916),  2500. 
Fr.  675.  C.  A.  10  (1916),  2501. 
Fr.  673. 
Fr.  666. 

C.  A.  11  (1917),  2600. 
Fr.  675. 
Fr.  663. 
Fr.  675. 


United  States  Patents. 


930,836. 
967,838. 
978,145. 
1,012,923. 
1,016,784. 
1,034,092. 
1,034,093. 
1,034,166. 
1,060,327. 
1,068,172. 
1,073,942. 
1,074,781. 

Busch. 
C.  A.  4 
C.  A.  5 
C.  A.  6 
C.  A.  6 
C.  A.  6 
Ibid. 
Ibid. 
C.  A.  7 
C.,A.  7 
C.  A.  7 
C.  A.  7 

(1910), 
(191t), 
(1912), 
(1912), 
(1912), 

(1913), 
(1913), 
(1913), 
(1913), 

2980. 
971. 
535. 
794. 
2674. 

2094. 
2995. 
3819. 
4046. 

,076,322. 
1,087,144. 
,087,145. 
,167,622. 
,180,694. 
1,244,901. 
1,247,270. 
1,259,517. 
1,269,792. 
1,271,846. 
1,315,543. 
1,315,546. 

C.  A. 
C.  A. 
Ibid. 
C.  A. 
C.  A. 
C.  A. 
C.  A. 
C.  A. 
C.  A. 
Ibid. 
C.  A. 
C.  A. 

8 
8 

10 
10 
12 
12 
12 
12 

13 
13 

(1914), 
(1914), 

(1916) 
(1916) 
(1918) 
(1918) 
U918) 
(1918) 

(1919) 
(1919) 

231. 
1337. 

,  805. 
,  1693 
,  155. 
,  280, 
,  1496 
,  1909 

,  2881 
,  2882 

588. 

British  Patents. 


24,981.  C.  A.  6  (1912),  1547. 

27,049.  C.  A.  5  (1911),  3127. 

28,049.  Ibid. 

28,583.  C.  A.  6  (1912),  1500. 


124.194.  C.  A.  13  (1919),  1595. 

124.195.  Ibid. 

125,000.    C.  A.  13  (1919),  1716. 


380  COMPOUNDS  OF  MERCURY 

Swiss  Patents. 

74,446.    C.  A.  11  (1917),  2027.  79,026.    Ibid. 

79,017.    C.  A.  13  (1919),  2418. 

French  Patents. 

402,740.    C.-A.  6  (1912),  1958.  479,656.    C.  A.  11  (1917),  870. 

404,491.    C.  A.  5  (1911),  1661. 

Dutch  Patents. 
1,179.    C.  A.  10  (1916),  1578. 

Canadian  Patents. 

181.655.  C.  A.  12  (1918),  588.  181,657.    Ibid. 

181.656.  Ibid. 

Swedish  Patents. 
43,001.    G.  A.  12  (1918),  484. 


INDICES 
SUBJECT  INDEX 


Absorption   of  light   by    C-Hg   compounds, 

162,  165,  185. 
Acetal,  ethoxyacrolein-,  with  mercuri-am- 

line,   216 ;   —   propargyl-,   with    Hg-ani- 

line,  213,  216. 
Acetaldehyde,  from  acetylene,  16,  33,  42  ; 

—  from  C-Hg  cpds,,  131 ;  — from  vinyl 
bromide,   121  ;  —  mercuri-,   68,   69,   78, 
154,  155  ;  —  dimercuri-,  119,  129,  154  ; 

—  trimercuri-,  118,  126,  155. 

Acetamide,   N-Hg-,   160,   164,   209,   373. 

Acetamino-benzoic  acid,  Hg-,  370  ;  —  phe- 
nol, Hg-,  275,  358;  --  salicylic  acid, 
Hg-,  319. 

Acetanilide,  Hg-,  56,  62,  72,  212,  213, 
219,  233  ;  —  nitro,  Hg-,  '221. 

Acetate  group,  quantitative  determination 
in  C-Hg  cpds.,  364. 

Acetic  acid,  with  C-Hg  cpds.,  87,  94,  104, 
185,  264,  267,  272  ; from  acety- 
lene, 16,  33  ; from  mercury  methyl, 

87;  —  -  mercuri-,  30,  45,  50,  70,  78, 
109,  111,  141,  145,  152  ; dimer- 
curi-, 110,  143; trimercuri-,  126, 

129,  131,  144. 

Acetic  anhydride,  with  C-Hg  cpds.,  211, 
288. 

Acetoacetic  ester,  Hg-,  16,  30,  152 ;  — 
sodium  derivative,  with  RHgX,  41. 

Acetone,  from  allylene,  16  ;  —  change  to 
Hg  isopropyl,  22,  101 ;  —  from  C-Hg 
cpds.,  119  ;  —  mercarbide,  157  ;  —  mer- 
curi-, 15,  51,  69,  77,  155,  156,  157,  158  ; 

—  trimercuri-,   119,   131 ;   —  reduction 
to  Hg  isopropyl,   158. 

Acetone  dicarboxylic  acid,  Hg-,  152. 

Acetophenone,  from  C-Hg  cpd.,  194 ;  — 
from  phenyl  acetylene,  194  ;  —  Hg-,  28, 
30,  35,  44,  50,  51,  72,  32*.  See  Phena- 
cyl  Hg-. 

o-Acetotoluidide,  mercuri-,  245  ;  —  dimer- 
curi-, 246. 

m-Acetotoluidide,  mercuri-,  246 ;  —  tri- 
mercuri-, 247. 

p-Acetotoluidide,  mercuri-,  247. 

Acetyl  acetone,  Hg-,  158 ;  —  anthranilic 
acid,  Hg-,  300;  —  chloride,  with  C-Hg 
cpds.,  82,  122,  255,  258,  260,  333. 

Acetyl  indandione,  Hg-,  326 ;  —  a-naph- 
thylamine,  Hg-,  250  ;  —  phenols,  Hg — , 
stability  of  C-Hg  linkage,  274  ;  —  sal- 
icylic acid,  Hg-,  317. 

Acetylation  of  C-Hg  cpds.,  211,  218,  219, 
221,  246,  274. 

Acetylene,  with  mercuric  salts,  16,  33,  42, 
46,  68,  71,  118,  129,  154,  376  ;  —  from 
mercury  ethyl  and  iodoform,  95 ;  — 
tetrabromide,  with  alkaline  mercuric 
cyanide,  121. 

Acetylenic  acids  and  esters,  with  Hg  salts, 
151. 

Acetylide,   Hg-,   55,   69. 

Acids,  with  alpha  mercuri-  cpds.,  41.  See 
Alpha  Hg- ;  —  with  C-Hg  cpds.,  14,  S9, 


41,  49,  87,  88,  90,  94,  100,  104,  106, 
120,  122,  126,  129,  132,  135,  138,  140, 
143,  145,  146,  147,  148,  152,  155,  156, 
167,  175,  182,  183,  184,  190,  192,  195, 
196  197,  198,  201,  203,  204,  208,  210, 
211  212,  217,  223,  225,  250,  255,  261, 
263,  267,  272,  274,  276,  281,  283,  284, 
291,  294,  299,  309,  314,  316,  317,  319, 
324,  325,  331,  344,  345,  346,  347,  348, 
353. 

Acids,  with  C-Hg  cpds.  derived  from  un- 
saturated  substances,  32,  34,  108,  109, 
110,  111,  113,  114,  120,  132,  133,  134, 
135,  137,  195,  286,  287,  331,  348;  — 
with  mercuri-formic  esters,  34  ;  —  with 
N-Hg  cpds.,  160. 

Acid  amides,  N-Hg-,  159,  373. 

Acid  anhydrides,  with  C-Hg  cpds.,  18,  111, 
168. 

Acid  anilides,   Hg-,   232.     See  Acetanilide. 

Acid  chlorides,  with  C-Hg  cpds.,  41,  57, 
81,  122,  167,  333. 

Acid  ureides,  with  C-Hg  cpds.,  319. 

Acoin,  369. 

Acridines,   Hg-,   343. 

Acrylic  acid,  with  Hg  salts,  74,  148,  149. 

Acyl  chlorides,  with  C-Hg  cpds.,  41,  57, 
81,  122,  167,  333. 

Acylation  of  C-Hg  cpds.,  82.  See  Acetyl- 
ation. 

Addition  of  basic  mercury  salts  to  2,  5- 
substituted  thiophenes,  36.  See  Thio- 
phene. 

Addition  of  basic  mercury  salts  to  unsat- 
urated  compounds.  See .  Unsaturated 
compounds,  Ethylene,  Allyl,  alcohol,  etc. 

Addition  compounds  containing  mercury, 
90,  251,  262,  263,  265,  284. 

Afridol,   368. 

Alanine,  double  cpds.  with  C-Hg  cpds., 
269. 

Albumen,  with  C-Hg  cpds.,  142,  279,  309, 
319;  —  Hg-,  356. 

Alcohol,  from  acetylene,  33  ;  —  with  Hg 
cpds.,  14,  30,  125. 

Alcohols,  tertiary,  Hg-,  324,  325. 

Alcoholysis  of  Hg  salts,  125. 

Aldehydes,  Hg-,  30,  154  ;  —  with  Hg-ani- 
lines,  212. 

Aliphatic  acids,  Hg-,  137  ;  —  amines,  Hg-, 
374  ;  —  nitro  cpds.,  Hg-,  123. 

Alkaline  reduction,  for  changing  RHgX  to 
R2Hg,  64.  See  Ferrous  hydroxide,  Stan- 
nite,  Hydrosulfite,  Mercuribis-,  etc. 

Alkaloids,  Hg-,  342  ;  —  with  Hg  salts,  376. 

0-Alkoxyl  hydrocinnamic  acids  and  esters 
from  C-Hg  cpds.,  33,  54,  311. 

Alkyl  anthranilic  acids,  Hg-,  300  ;  —  bro- 
mides, with  sodium  amalgam,  14.  See 
Sodium  amalgam  ;  —  halides,  with  C-Hg 
cpds.,  32,  41,  19,  80,  115,  137,  138,  139, 
215,  224,  226,  335  ;  —  halides,  with  Hg 
cpds.  derived  from  unsaturated  sub- 
stances, 80,  110,  114,  137,  335;  — 


381 


382 


INDICES 


halides,    secondary    and    tertiary,    with 

C-Hg  cpds.,   335  ;   —  iodides,   with   me- 
tallic mercury,  13,  89.     See  Mercury. 
Alkyl   iodides,   with   sodium   amalgam,   14. 

See   Sodium   amalgam. 
Alkyl  mercury  compounds,  85. 
Alkyl   mercuri-,   free  radicals,   preparation 

by  electrolysis,  23. 
Allene  mercuri-  cpds.,  132. 
Allocinnamic  acid,  with   Hg  salts,  23,  32, 

54,   148,   309. 
Allyl  acetoxime,  Hg-,  158  ;  —  alcohol,  with 

Hg  cpds.,  32,  76,  77,  82,  126,  181,  132, 

133. 
p-Allyl    anisole,    with    Hg    salts,    285  ;    — 

catechol,  dimethyl  ether,  with  Hg  salts, 

287  ;  —  catechol,  methylene  ether,  with 
•    Hg  salts,   286. 
Allyl   chloride,   from  C-Hg  cpds.,   134 ;  — 

cinnamate,  with  Hg  salts,  312  ;  —  ether, 

from  C-Hg  cpds. 
Allyl  cpds.  of  phenol  ethers,  with  Hg  salts, 

22,  284. 
Allyl  iodide,  with  C-Hg  cpds.,  80,  94,  98, 

123,  129,  169  ; with  metallic  mer- 
cury, 14,  26,  122. 
Allyl   mercuri-    cpds.,    14,    26,    50,   55,    67, 

78,   79,  82,   91,    122. 
Allyl  pyridine,  with  Hg  salts,  375. 
Alpha    mercuri-   cpds.    (mercury    attached 

to  carbon  alpha  to  carbonyl  group),  37, 

41,  44,  45,  47,  50,  51,  55,  324,  344,  345, 

346,  347,  348. 

Alpha   halogen  esters,   with    sodium   amal- 
gam,  22. 

Allylene,  with   Hg  salts,  16,  81,  119. 
Aluminum,   with    C-Hg  cpds.,    84,   87,    93, 

100,  102,  166. 
Aluminum  alkyls,  from  C-Hg  cpds.,  84  ;  — 

isobutyl,  102  ;  —  ethyl,  93  ;  —  methyl, 

87  ;  —  phenyl,  84,  166  ;  —  propyl,  100. 
Aluminum  carbide,  with  Hg  salts,  24,  86, 

89. 

Amalgams.      See   Sodium   amalgam. 
Amides,  N-Hg-,  159,  373. 
Amines,  with  Hg  salts,  374. 
Amines,  aromatic,  Hg-,  205.     See  Aniline, 

etc. 

Amino  acids,  with  Hg  salts,  1 59,  374. 
a-Amino  acids,  with  C-Hg  cpds.,  319. 
Amino  aryl  sulfonic  acids,  Hg-,  250. 
Amino    azo   cpds.,   arsonic    acids   of-,   Hg-, 

359. 
Amino    benzoic    acids,    Hg-,    57,    61,    296, 

303,  304,   307,   355. 
p-Amino    benzoic   acid,   Hg-,   diazotization, 

320. 
a-Amino  isobutyric  salts,  with  C-Hg  cpds., 

319. 
m-Amino-p-hydroxy-phenyl      dichloro      ar- 

sine,  change  to  C-Hg  cpd.,  274. 
m-Amino     malachite    green,     diazotization 

and  coupling  with  Hg-phenol,  256,  354. 
Amino  methane  disulfonic  acid,   Hg-,   153. 
1,    8-Aminonaphthol-4-sulfonic    acid,     Hg., 

281. 
1,     8-Aminonaphthol-3,    6-disulfonic    acid, 

Hg-,  282. 
1,     8-Aminonaphthol-4,     6-disulfonic    acid, 

Hg-,    281. 

Amino  nitroso  benzene,  Hg-,  218. 
/J-Amino-a-hydroxy-isobutyric     salts,     with 

C-Hg  cpds.,  58,  319. 
Amino    phenols,    Hg-,   59,    274,  275. 
Amino  phenol  sulfonic  acid  III,  Hg-,  275, 

Oi-Ainino  phenol  arsonic  acid,  Hg-,  358. 


5-Amino  salicylic  acid,  Hg-,  319. 
Ammonia,     liquid,    as    solvent    for    C-Hg 

cpds.,  88. 
Ammonia,  with  RHgX,  109,   133,   164;  — 

with    Hg-nitrosophenol,   218. 
Ammonium,  di  (phenylmercuri-),  177. 
Ammonium  bromide,  with  N-Hg  cpds.,  233, 

251. 
Ammo'nium    carbonate,    with    C-Hg    cpds., 

298. 
Ammonium    hydroxide,    with    C-Hg    cpds., 

48,    65,    177,    219,    227,    242,    243,    245, 

247,  284,  287,  336,  356  ; for  chang- 
ing RHgX  to  RuHg,  245. 
Ammonium   sulflde.      See   Sulfides. 
Ammonobasic   salts,   249. 
iso-Amyl  acetate,  from  C-Hg  cpds.,  87,  104. 
Amyl  alcohol,   as   solvent  for  C-Hg  cpds., 

66,   198. 
iso-Amyl  Hg-  cpds.,  27,  42,  65,  67,  84,  87, 

103. 

Amylene,  with  Hg  salts,  117. 
Analysis  of  C-Hg  cpds.,  361  ff. 
Anethole.  oxidation  by  Hg  salts,  285. 
Anhydrides    or    inner    salts    of    hydroxy- 

mercuri-  acids,  49. 
Anhydrides    or   inner   imides    of    hydroxy- 

mercuri-  cpds.  of  amines,  247,  256. 
Anilides,   Hg-.     See  Acetanilide. 
a-Anilido   acids   and   esters,    Hg-.   23,    236, 

238,  239,  240. 
Aniline,    compounds   with    Hg   salts,    205 ; 

—  as  a  solvent  for  C-Hg  cpds.,  200  ;  — 
with  N-Hg-acetamide,  210  ;  —  mercuri-, 
13,  17,  35,  47,  56,  60,  61,  62,  66,  72,  81, 
82,  205  ff.,  355,  375  ;  —  dimercuri-,  219. 

Aniline,  Hg-,  with  acetic  anhydride,  212  ; 
-  acetylation,  212,  219,  221;  —  with 
aldehydes,  212  ;  —  with  ammonium  hy- 
droxide, 219.  See  Ammonium  hydrox- 
ide. 

Aniline,  Hg-,  diazotization,  212,  355;  — 
with  dinitrophenyl  pyridinium  chloride, 
212,  216,  218 ;  —  with  ethoxyacrolein 
acetal,  216  ;  —  with  methyl  iodide,  215, 
222,  224 ;  —  with  propargyl  acetal, 
216. 

Aniline  arsonic  acids,  Hg-,  357. 

Anilino  acids.      See   Anilido    acids. 

Animal  experiments  with  C-Hg  cpds.,  307. 
See  Pharmacological,  Medical,  etc. 

Anisic  acid,   Hg-,   320. 

Anisole,  Hg-,  64,  66,  78,  81,  262  ff.  See 
Anisyl. 

p-Anisyl  antimony  cpds.,  change  to  C-Hg 
cpds.,  264. 

p-Anisyl  dichloro  arsine,  from  C-Hg  cpd., 
265. 

o-Anisyl  Hg-  cpds.,   64,   262. 

p-Anisyl  Hg-  cpds.,  17,  28,  263,  264,  265. 
See  Anisole. 

p-Anisyl  indole,  Hg-,  342. 

Anogon,    368. 

Anthracene,   Hg-,  36. 

Anthranil,    from   C-Hg    cpd.,    44,    192. 

Anthranilic  acids  and  esters,  Hg-,  23,  56, 
72,  75,  296,  299. 

Antimony,  with  C-Hg  cpds.,  170  ;  —  ani- 
syl,  change  to  C-Hg  cpd.,  264 ;  — 
chloride,  with  C-Hg  cpds.,  87,  167,  172  ; 

—  phenetyl,  change  to  C-Hg  cpd.,  268  ; 
—  phenyl,  from  C-Hg  cpd.,  171. 

Antipyrine,   with    Hg  salts,   345,   348. 
Apiol,  with   Hg  salts,  285,   288. 
Apparatus,    for    determination    of    Hg    in 

C-Hg  cpds.,   365. 
Aqua  regia,  with  C-Hg  cpds.,  126, 


SUBJECT  INDEX 


383 


Aromatic  acids,  Hg-,  290  ff.  ;  —  amines, 
Hg-,  205  ff ;  —  with  Ilg  salts,  205,  375, 

Aromatic  arsenoxides,  with  Hg  salts,  37  ; 
— mercury  cpds.,  163  ff;  —  nitro  cpds., 
Ilg-,  189  ;  — -  sulfur  cpds.,  with  Hg  salts, 
376  ;  —  tellurides,  with  Hg  salts,  376. 

Arrhenal,  309. 

p-Arsanilic   acid.   Hg-,   357,    368. 

Aryl  halides,  with  C-Hg  cpds.,  79. 

Aryloxy  fatty  acids,  Hg-,  269. 

Arsenate,  Hg-,  101. 

Arsenic  cpds.,  organic,  containing  Hg,  S56. 

Arsenic  cpds..  replacement  of  As  by  Hg, 
238,  271.  274. 

Arsenious  chloride,  with  C-Hg  cpds.,  41, 
78.  95.  167,  172,  176,  179,  182,  186,  190, 
199.  203,  265,  334. 

Arsenious  iodide,  with  C-Hg  cpds.,  335 ; 
—  oxide,  p-aminophenyl-,  with  Hg  cpds., 
213;  —  sulflde,  phenyl-,  with  Hg  ethyl, 

Arsenobenzene,   with   Hg  ethyl,  95. 
Arseno   cpds.,   change   to   C-Hg  cpds.,   238. 
Arsenoxides,  aromatic-,  with  Hg  cpds.,  37. 
Arsine,    /3-naphthyl    dichloro-,    from    C-Hg 

cpd.,    203 ;    -  -    phenyl    dichloro-,    from 

C-Hg  cpd.,  16  ;  —  phenyl  diethyl-,  from 

C-Hg  cpd.,  95. 

Arsinic  acids.     See  Arsonic  acids. 
Arsonic    acids,    Hg-,    275,    320.    357,    368, 

369 :   —   of  nitro   phenols,    Hg-,   62  •  — 

of  phenols,   Hg-,  64. 
Asarone,  oxidation  by  Hg  salts,   285. 
Asbestos,  gold  coated,  for  det.  of  Hg,  361. 
Asiphyl.    368. 
Aspirochyl.    368. 
Asterol.    279,    368,    369. 
Asurol.   368. 
Atoxiphil.    368. 
Atoxyl,    Hg-,    368. 
Azides,    140. 
Azodicarboxylic   ester,    from    Hg    cpd.,    70, 

Azonaphthols,    Hg-.    352. 

Azophenols,    Hg-,    352. 

Azophenol  arsonic  acids,  Hg-,  359. 

Barbital.  with  C-Hg  cpds.,  161,  269,  312 
319,  370. 

Bases,  formation  during  splitting  of  C-Hg 
linkage  by  halides,  73,  75,  150  151 
251.  256,  259.  280 ;  —  for  changing 
RHgX  to  R2Hg,  64,  86;  —  splitting 
C-Hg  linkage  Ify,  261. 

Bases,  with  C-Hg  cpds.,  39,  47,  48,  49,  52, 
65.  110,  111.  112.  113,  116,  127,  129 
131,  134,  135,  136,  138,  144,  145,  146 
147,  148,  152,  153,  154,  155,  156,  176* 
190,  204,  213,  214,  217,  219,  221  227 
231,  234,  237.  250,  251,  252,  254'  259' 
261,  264.  267,  272,  273,  275,  278'  280' 
282.  283,  284,  287,  294,  295,  296,  298' 
301,  307,  309,  312,  319,  320,  327,  330 
336.  356,  359,  362  ;  —  with  C-Hg  cpds. 
derived  from  unsaturated  substances 
286.  See  Zinc  and  bases. 

"Basic  mercuric  benzoate,"   35. 

"Basic  mercuric  salicylate,"  316 

Beer   yeast,   with    Hg   cpds.,   369. 

Benzal  chloride,  with  C-Hg  cpds.,  79,  169 

p-Benzarsonic  acid,   Hg-.  359. 

Benzene,   mercuration   of,    35. 

Bonzeneazo  cpds..  from  Hg-phenols  and 
dinzo  cpds.,  20. 

Bonzeneazo-p-cresol,  Hg-,  276  :  naphthols, 
Ilg-.  353;  phenols,  Hg-,  255,  258,  259, 
,3o2,  355. 


Benzene  diazonium  salts,  from  C-Hg  cpds., 
18,  168  ;  —  sulflnic  acid.  See  Sulfinic 
acids ;  —  sulfone  chloride,  with  C-Hg 
cpds.,  83,  167  ;  —  sulfonic  acid,  Hg-, 
194. 

Benzidine,  Hg-,  349 ;  —  sulfonic  acid, 
Hg-,  349;  —  disulfonic  acid,  Hg-,  349. 

Benzoate,  Hg-,  effect  of  heat,  35,  290,  331. 

Benzoic  acid,  from  C-Hg  cpd.,  93  ;  —  mer- 
curi-,  35,  56,  64,  71,  75,  79,  290,  321. 

Benzoic  acids,  substituted,  Hg-,  with  sul- 
fides,  56. 

Benzoic  esters,  Hg-,  57,  62,  292. 

Benzonitrile,  with  Hg  salts,  375. 

Benzophenone,   Hg-,  57,   325. 

Benzosulfonic    acid,    Hg-,    309. 

Benzoyl  chloride,  Hg-,  57,  79,  291,  294; 
-  with  C-Hg  cpds.,  82,  83,  122,  133, 
260,  273,  277,  288,  333,  336 ;  —  with 
N-Hg  cpds.,  245. 

Benzoylation  of  Hg-phenols,  255.  See 
Schotten-Baumann  reaction. 

Benzyl  acetate,  from  C-Hg  cpd.,  24,  87, 
•185;  —  alcohol  from  C-Hg  cpd.,  24, 
87,  185  ;  —  amine,  Hg-,  249. 

p-Benzylamino-phenyl  arsonic  acid,  Hg-, 
357 ;  —  w-nitrophenyl  arsonic  acid, 
Hg-,  357. 

Benzyl-aniline,  Hg-,  249  ;  —  boric  acid, 
change  to  C-Hg  cpd.,  15  ;  —  bromide, 
with  sodium  amalgam,  15  ;  —  chloride, 
with  C-Hg  cpds.,  81,  135,  257  ;  —  ethyl 
amine,  with  Hg  salts,  249  ;  —  halides, 
with  sodium  amalgam,  15,  28 ;  —  Hg- 
cpds.,  15,  24,  29,  35,  42,  66,  87,  184; 

—  methyl  amine,  with  Hg  salts,  249. 
Beryllium,   with   C-Hg   cpds.,    8-'f,  94,   100; 

—  alkyls,  from  C-Hg  cpds..  84,  100  :  — 
ethyl,  94. 

Bibliographical  lists,  miscellaneous,  376. 

Bibliography.* 

Biological  studies,  references,  371. 

Biphenyl,  brqmo-,  with  sodium  amalgam, 
204  ;  —  dibromo-,  with  sodium  amal- 
gam, 204  ;  —  from  C-Hg  cpds.,  166,  167, 
175;  —  Hg-,  28,  43,  204. 

Bismuth  organic  cpds.,  84  ;  —  with  C-Hg 
cpds.,  84,  94,  166,  170  ;  —  ethyl,  change 
to  C-Hg  cpd.,  13,  92,  94,  96,  97 ;  — 
from  C-Hg  cpds.,  84 ;  —  phenyl,  from 
C-Hg  cpd.,  166. 

Bisulfites,  with   C-Hg  cpds.,   127. 

Bisulfite,   Hg-,  with  aldehydes,  155. 

Boric  acids,  aromatic,  change  to  C-Hg 
cpds.,  17,  37,  171,  179,  180,  182,  185. 

Boron  halides,  with  C-Hg  cpds.,  40,  78, 
166,  179,  182. 

Bridging  reaction,  change  of  RHgX  to 
RL,Hg.  See  Mercuribis-  cpds. 

British   Patents,  379. 

Bromides,  with  sodium  amalgam.  See 
Sodium  amalgam. 

Bromine,  with  C-Hg  cpds.,  86,  93,  96,  100, 
101,  102,  103,  140,  148,  157,  173,  180, 
190,  196,  197,  198,  200,  218,  223,  231, 
236,  273,  291,  324,  336,  351,  352 ;  — 
with  C-Hg  cpds.  derived  from  unsat- 
urated cpds.,  196,  197,  280,  283,  291, 
298. 

AVBromo-acetamide,  with  C-Hg  cpds.,  170. 

*  For  a  formal  bibliography  see  Journal 
of  Industrial  and  Engineering  Chemistry, 
11  (1919),  1083.  The  references  in  the 
bibliography  are  contained  in  the  present 
monograph  and  are  made  available  by  this 
index. 


384 


INDICES 


0-Bromo-acetanilide,  from  C-Hg  cpd.,  218. 

Bromo-acetic  ester,  with  C-Hg  cpds.,  80, 
94,  97 ;  —  acetophenone,  from  C-Hg 
cpd.,  72,  324  ;  —  acetylene,  Hg-,  119. 

p-Bromo-aniline,  Hg-,  248 ;  —  arsonic 
acid,  Hg-,  357. 

o-Bromo-anisole,  with  sodium  amalgam, 
262. 

p-Bromo-anisole,  with  sodium  amalgam, 
17,  28,  263. 

Bromo-benzene,  with  sodium  amalgam,  15, 
163. 

o-Bromo-benzoic  acid,  from  C-Hg  cpd.,  71, 
180,  291. 

Bromo-biphenyl,  with  sodium  amalgam, 
28,  204. 

p-Bromo-diethylaniline,  with  sodium  amal- 
gam, 28,  231  ;  —  dimethylaniline,  Hg-, 
60,  227,  265  ;  —  with  sodium  amalgam, 
17t  28,  223. 

p-Bromo-dimethyl-p-toluidine,  with  sodium 
amalgam,  28,  245. 

Bromo-dinitro-pttenol,  from  C-Hg  cpd., 
273 ;  —  diphenyl,  with  sodium  amal- 
gam, 28,  204 ;  —  formic  ester,  from 
C-Hg  cpd.,  70,  140. 

a-Bromo-naphthalene,  from  C-Hg  cpd.,  73  ; 

—  with  sodium  amalgam,  14. 
/?-Bromo-naphthalene,    with    sodium    amal- 
gam, 202. 

o-.  m-,   and   p-Bromo-nitro-benzenes,   from 

C-Hg  cpds.,  190,  191. 
Bromo-phenetoles,   with    sodium   amalgam, 

28. 

3-Bromo-5-nitro-salicylic  acid,   Hg-,  319. 
Bromo-phenols,    from   C-Hg   cpds.,   71,   84. 
p-Bromo-phenol,    Hg-,   270. 
Bromo-phenylglycine    esters,     from    C-Hg 

cpds.,   72,   236. 

Bromo-phenyl    trimethyl   ammonium    chlo- 
ride, from  C-Hg  cpd.,  72. 
Bromo-thiophenes,    from    C-Hg,    336,    337. 
Bromo-toluenes,    from    C-Hg    cpds.,     180, 

183. 
Bromo-toluenes,  with  sodium  amalgam,  15, 

180,   181. 

Bromo-xylene,  with  sodium  amalgam,  186. 
Butane,  from  Hg  ethyl,  93. 
Butanol,    Hg-,    116. 
/3-iso-Butoxy-hydrocinnamic       acid,       from 

C-Hg  cpd.,  315. 

tso-Butyl  alcohol,  with  Hg  salts,  125. 
tertiary-Butyl    iodide,     with     C-Hg    cpds., 

335. 
t#o-Butyl   mercuri-   cpds.,   15,    27,    67,    84, 

101. 
sec-Butyl  mercuri-  cpds.,  22,  27,  67,  102; 

—  from  methyl  ethyl  ketone,  22. 
teo-Butylene,  with  Hg  salts,  32,  116,  117. 
Butyramide,   N-Hg-,   161. 
Butyratemercuri-  cpds.,  202,  268. 
Butyrates,  change  to  mercarbides,  129. 
Butyric  acid.      See  Amino-:  —  Hg-,   148  ; 

-  with   C-Hg  cpds.,   198,   202,   268. 
Butyric  acid,  0-hydroxy-,  from  C-Hg  cpd., 

54 ;    —   a-mercuri-j8-hydroxy,    54. 
Butyrone,  from  C-Hg  cpd.,  120. 

Cadmium,  with  C-Hg  cpds.,  84,  87,  93, 
166;  —  ethyl,  from  C-Hg  cpd.,  93;  — 
iodide,  with  C-Hg  cpds.,  87  ;  —  organic 
cpds.,  84  ff ;  —  phenyl,  166. 

Camphene,  from  C-Hg  cpds.,  332  ;  —  mer- 
curi-, 55,  331. 

Camphocarboxylic  acid,  Hg-,  331. 

Camphor,  mercuri-,  45,  330 :  dimercuri-, 
330. 


Camphorimide,    N-Hg-,    161. 

Camphorquinone,  from  C-Hg  cpds.,  73. 

Canadian  Patents,  380. 

Carbethoxy  indandione,  Hg-,  326. 

Carbide,  aluminum,  with  Hg  salts,  86. 

Carbon,  det.  in  C-Hg  cpds.,  361,   S63. 

Carbonatemercuri-  cpds.,  99,  112,  136, 177. 

Carbonates,  with  C-Hg  cpds.,  264,  269. 

Carbon  disulflde,  in  changing  RHgX  to 
R2Hg,  65,  164,  178  ;  —  with  N-Hg  cpds., 
208. 

Carbon  monoxide,  from  C-Hg  cpds.,  34,  81, 
137  ;  —  with  Hg  salts  in  alcohol,  33, 
34,  137. 

Carboxyl  group,  replacement  by  Hg,  21, 
25,  37,  191,  193. 

o-Carboxylphenyl  glycine,  Hg-,  302. 

Carvacroxy-acetic  acid.  Hg-,  269. 

Catechol,  with  Hg  salts,  282 ;  —  mono- 
methyl  ether,  Hg-,  59,  282 ;  —  o-car- 
boxylic  acid,  from  C-Hg  cpd.,  72. 

Catechoxy-acetic  acid,  Hg-,   269,  369. 

Cellulose,    with    Hg   cpds.,    126. 

Chaulmoogra  oil  and  esters,  with  Hg  salts, 
150. 

Chloral,   from   C-Hg  cpds.,   68. 

Chloratemercuri-  cpds.,   154. 

Chlorate,  Hg-,  with  acetylene,  69. 

Chlorides,  with  C-Hg  cpds.,  253,  280,  284. 
291,  298. 

Chlorine,  with  C-Hg  cpds.,  52,  93,  103, 
121,  127,  165,  172. 

Chlorine  monoxide,  with  C-Hg  cpds.,  168. 

Chloro-acetone,  with  Hg  salts,  158. 

Chloro-acetylene,  from  C-Hg  cpd.,  78 ;  — 
mercuri-,  78,  119,  144. 

p-Chloro-o-amino-phenol,   Hg-,   275. 

o-Chloro-benzoic  acid,  Hg-,  56,  295. 

m-Chloro-benzoic  acid,   Hg-,   295. 

Chlorocyanogen,  with  C-Hg  cpds.,  83,  188. 

Chloroform,  with  C-Hg  cpds.,  80. 

Chloroformic  ester,  with  C-Hg  cpds.,  83, 
163,  188  ;  —  with  sodium  amalgam,  15. 

Chloromethyl  mercuri-  cpds.,  68,   106. 

0-Chloro-naphthalene,  with  sodium  amal- 
gam, 202. 

p-Chloro-o-nitro-phenol,   Hg-,  275. 

o-Chloro-phenol,  Hg-,  269,  370. 

p-Chloro-phenol,   Hg-,  270. 

Chloro-phenoxyacetic  acids,  Hg-,  269,  368, 
370. 

a-Chloro-thiophene,  Hg-,  337. 

Chloro-triiodo-ethylene,    from    C-Hg    cpd., 

Cho'lic  acid,  Hg  salt,  369. 
Chromate,  Hg-,  with  acetylene,  68. 
Chromic  acid,   with   C-Hg  cpds.,   126. 
Cineol    iodide,    from    C-Hg    cpd.,    73 ;    — 

mercuri-,    64,    73,    326,   327,    328. 
Cinnamic  acid,   from   Hg.   cpd.  of  allocin- 

namic  acid,  54,  310  ;  —  from  phenyl  hy- 

dracrylic   acid,   310  ;  —  with   Hg  salts, 

23,  32,   309. 
Cinnamic   acid,    allo-,    with    Hg    salts,    23, 

32,    309;    —    ester,    with    Hg    salts    in 

alcohols,  23,  33,  .46,  149,  3 11. 
Cis  unsaturated  acids,  with   Hg  salts,  23, 

32,    149,    310. 
Citraconic   acid,    with    Hg   salts,    74,    148, 

151. 

Citric   acid,   with   Hg  salts,   153. 
Collidines,  with  Hg  salts.  375. 
Color    of   C-Hg    cpds.,    22,    124,    221,    222, 

229,  231,  242,   272,  273,   274,  280. 
Combustion  of  C-Hg  cpds.,  363. 
Complex  metals,  RHg-,  88,  96, 
Contraluesin,   368. 


SUBJECT  INDEX 


385 


Copper,   in  changing  RHgX  to  R2Hg,  65; 

—  with    C-Hg   cpds.,    65,    83,    94,    142, 
166,  198  ;  —  salts  of  mercuri-acids,  238. 

Coupling    of    anilines    and    phenols    with 

mercuri-diazonium  salts,   212. 
Coupling   mercuri-phenols  with   diazonium 

salts,   255. 
»-Cresol,  mercuri-,  275  ;  —  dimercuri-,  275, 

277. 

o-Cresol  arsonic  acid,  Hg-,  275,  358. 
p-Cresol   methyl  ether,   Hg-,   277. 
o-Cresol-phthalein,    Hg-,    322. 
p-Cresoxy-acetic  acid,  Hg-,  269. 
Crotonic    acid,    from    C-Hg    cpd.,    54 ;    — 

with  Hg  salts,  74,  148,  150. 
Cyanamide,    with     C-Hg    cpds.,     178;    — 

di(phenylmercuri-),  178. 
Cyanates,  from  RHgCN  and  bases,  176. 
Cyanide,  Hg-,  22,  162. 
Cyanides,  in  changing  RHgX  to  R2Hg,  40, 

85,  92.  98  :  —  with  C-Hg  cpds.,  77,  113, 

119,   120,   122,   126,   127,   131,   132,   135, 

143,    145,    146,    152,    156,    283,    298;    — 

with    C-Hg    cpds.    derived    from    unsat- 

urated    substances,    120,    132 ;    —    with 

mercarbides,  43,   53  ;  —  with   mercuric 

salts,   374. 
Cyanomercuri-    cpds.,    98,    101,    136,    174, 

176,    186,    189,    265,    268. 
Cyano-acetamide,    Hg-,    160 ;    acetic    acid, 

Hg-,  50,  74  ;  —  acids,  Hg-,  159. 
Cyanogen    chloride,   with    C-Hg   cpds.,    83, 

188  ;  —  iodide,  with  C-Hg  cpds.,  86  ;  — 

from  C-Hg  cpd.,   176. 
Cyclo-.     See   Hexyl,   etc. 
Cyclohexane,   Hg-,    188. 
Cyclohexyl  iodide,   with   sodium  amalgam, 

27. 

Cycloliexyl  Hg-  cpds.,  27,  29. 
Cyclo-mercuri-pentamethylene,   28,   64,   65, 

351. 

Cyclo-mercuri-polymethylenes,  349. 
Cyclo-mercuri-tetramethylene,  350. 
Cyclopentadiene,  with   Hg  salts,   120. 
p-Cymene,   Hg-,  28,   83,  188. 

Determination  of  Hg  as  metal,  361,  365. 
Determination  of  position  of  Hg  in  C-Hg 

cpds.      See    Halogens,    Bromine,    Iodine, 

Diazonium   salts,  etc. 

Diallyl,  from  C-Hg  cpd.,  79,  94,  122,  169. 
Diamines,  with  Hg  salts,  374. 
o-,   o'-,   Diauiinophenol   arsonic   acid,    Hg-, 

358. 

Diazoacetic  ester,  Hg-,  51,  69,  80,  83,  162. 
Diazonium  salts,  from  C-Hg  cpds.,  18,  168, 

179,  182  ;  —  with  C-Hg  cpds.,  258,  259, 

276,   281  ;   —  with    Hg-naphthols,    354 ; 

-  with    Hg-phenols,   20,   255,   354. 
Diazosulfanilic  acid,  with  C-Hg  cpds.,  253, 

280,   355. 
Diazotization    of    Hg-anilines,    212,     307, 

320,  355. 

Dibenzyl,  from  C-Hg  cpd.,  173,  185. 
Dibromides,  with  sodium  amalgam,  23,  24, 

204,  350. 
Dibromo-acetic  ester,  from  C-Hg  cpd.,  148  ; 

—  acetone,   from   C-Hg   cpd.,   69,    157 ; 

-  acetophenone,   from   C-Hg   cpd.,   69 ; 

—  acetylidine,    121. 

S,  5-Dibromo-benzoic  acid,   Hg-,  295. 
Dibromo-diphenyl,   with    sodium   amalgam, 
28,   204;   —  fluorescein,   Hg-,   323,   370; 

—  nitro-acetic   ester,    from    C-Hg   cpd., 
69. 

Dibromo-p-nitro-ethylaniline,     from     C-Hg 
cpd.,  231  ;  —  p-nitro-methylaniline,  from 


C-Hg  cpd.,  223;  —  pentane,  with  so- 
dium amalgam,  351 ;  —  phenol,  Hg-, 
270  ;  —  thiophene,  from  C-Hg  cpd.,  73. 

Dibutyl  ketone,  with  Hg  salts,  158. 

Dichloro-phosphines,  from  C-Hg  cpds.,  78. 

Dicyandiamide,  from  N-Hg  cpd.,  208 ;  — 
with  C-Hg  cpds.,  319. 

Di-cyclopentadiene,  with  Hg  salts,  77,  120. 

Diethylaniline,  Hg-,  28,  56,  231 ;  —  with 
diazotized  Hg-aniline,  212,  356. 

Diethyl  barbituric  acid,  with  C-Hg  cpds., 
161,  269,  312,  319,  370  ;  —  ketone,  with 
Hg  salts,  158;  —  pyridine,  with  Hg 
salts,  375. 

Diepiiodohydrine,    from    C-Hg    cpd.,    136 ; 

—  dimercuri-,  63,  68,  81,  132,  133. 
Dihalides,  with  sodium  amalgam,  27,  350. 
Dihydrocinnamic    acid,    0-hydroxy-,    from 

C-Hg  cpd.,  54. 
Dihydronaphthalene,    with    Hg    salts,    47, 

204. 
Dihydroxybenzenes,  with  Hg  salts,  59,  282. 

1,  8-Dihydroxynaphthalene-3,    6-disulfonic 
acid,   with   Hg  salts,  282. 

Diiodides,  with  sodium  amalgam,  350. 
Diiodo-o-acetotoluidide,    from    C-Hg    cpd., 

246. 
Diiodo-m-acetotoluidide,    from    C-Hg    cpd., 

246. 
Diiodo-acetylene,  from  C-Hg  cpd.,  69,  71 ; 

—  aniline,  from  C.-Hg  cpd.,  72,  209  ;  — • 
butane,  with  sodium  amalgam,  350  ;  — 
camphor,    from    C-Hg,    73 ;    —    diethyl 
ether,  from  C-Hg  cpd.,  32,  46,  68,  108, 
111  ;   —  phenol,   from  C-Hg  cpd.,   259 ; 

—  sulfonic    acid,    Hg-,    368 ;    —    thio- 
phene,   from    C-Hg    cpd.,    73,    336 ;    — 
tyrosin,   Hg-,   321. 

Dimercuri  cpds.,  242. 
Dimethylamino-phenyl  Hg-  cpds.,  17,  274  ; 

—  phosphenyl  chloride,  from  C-Hg  cpd., 

Dimethyl-aniline,  Hg-,  17,  28,  56,  223; 
—  with  diazotized  Hg-aniline,  212,  356  ; 

—  with    Hg  salts,    17 ;   —  w-hydroxy-, 

Dimethyl  anthranilic  acid,  Hg-,  302. 

2,  5-Dimethyl  benzoic  acid,  Hg-,  309. 

3,  //-Dimethyl  benzoic  acid,  Hg-,  321. 
s.?/m-Dimethyl  ethylene,  with  Hg  salts,  117. 
Dimethyl    ethyl   ethylene,    with    Hg   salts, 

Dimethyl  heptenol,  with  Hg  salts,  33,  48, 
329  ;    —    &  -  naphthylamine  -  6  -  sulfonic 
acid,  with   Hg  salts,  253  ;  —  pyridines 
with   Hg  salts,  375  ;  —  thiophene,  Hg-, 
339  ;  —  p-toluidine,  Hg-,  28,  244. 
aa'-Dinaphthyl,  from  C-Hg  cpd.,  198 
00'-Dinaphthyl,  from  C-Hg  cpd.,  203. 

2,  4-Dinitro  benzoic  acid,  Hg-,  64  ;  —  from 

3,  5-Dinitro'  benzoic  acid,   Hg-,   296. 
2,  4-Dinitro  benzyl,   Hg-,  cpds.,   193 
Dinitro    phenol,    Hg-,    82,    272. 

o-,  o'-Dinitrophenol  arsonic  acid,-Hg-,  358. 

2,  //-Dinitrophenyl  acetic  acid,   change   to 
C-Hg   cpd.,    193. 

Dinitrophenyl  pyridinium  chloride,  with 
Hg-anilines,  212,  216,  218,  244. 

3,  5-Dinitro  salicylic  acid,    Hg-,   319. 

o-,  o'-Dinitro  tolane,  from  C-Hg  cpd.,  192 
Dinitro  toluene,  Hg-,  44,  193. 
Diphenyl.     See  Biphenyl. 
Diphenylamine,  mercuri-,  45,  61 ;  —  tetra- 

mercuri-,  234. 
Diphenyl  antimony  trichloride,  from  C-Hg 

cpd.,  167. 


386 


INDICES 


Diphenyl  bromide,  with  sodium  amalgam, 
204     —  chloro  arsine,  from  C-Hg  cpd., 


cpd. 
cpd. 


—  dibromide,  with  sodium  amal- 
204 ;  —  guanidine,  from  N-Hg 
209 ;  —  iodonium  chloride,  from 


167 
gam 
cpd. 
C-Hg  cpd.',  170;  —  sulfide,  from  C-Hg 


170,   176 ;   —  sulfone,   from  C-Hg 
83;  —  tin  dichloride,   166. 


Dipropylene  oxide   Hg-  cpds.,   131,    13S. 
Dipropyl  ketone,  from  C-Hg  cpd.,  120 ;  — 

with  Hg  salts,  158. 
Dipyridyl,  with  Hg  salts,  375. 
Dithienyl  chloro   arsine,   from   C-Hg  cpd., 

334. 

Dithiocarbamines,   Hg-,   161. 
Ditolyl,  from  C-Hg  cpd.,  182. 
Double  cpds.   containing  Hg,   17,   59,  205, 

207,  221,   227,   230,  232,   242,  249,   330, 

356,  S7Jf,  376. 
Double  ends,  of  aniline  with  llg  salts,  217  ; 

—  of   Hg-salicylic   acid,   319;   —  of   N 

cpds.  with  C-Hg  cpds.,  370. 
D.R.P.,   378. 
Dutch    Patents,    380. 
Dyes,   Hg-,  24,   212,   355. 

Egole,  370. 

Electronic  Theory   of  C-Hg  cpds.,   24,   42. 

Electrolysis  of  RHgX,  23,   88,  362. 

Electrolytic  reduction  of  ketones,  forma- 
tion of  R2Hg,  101,  102. 

Embarin,   369. 

Enesol,   369. 

Erythrosin,  from  C-Hg  cpd.,  323. 

Esters,  as  catalysts  in  making  R2Hg  from 
RX  and  sodium  amalgam,  14,  15,  17, 
26,  27,  85,  91,  101,  103,  163,  197,  202, 
245. 

Esters,   with   hydroxymercuri-   cpds.,    228. 

Ethane,  from  C-Hg  cpd.,  14,  87. 

Ethane  hexamercarbide,  19,  30,  43,  52, 
76,  77,  79,  80,  125,  128. 

Ethanol  mercuri-  cpds.,  101,  108,  141. 

Ether  mercury  cpds.,  48,  53,  54,  55,  62, 
63,  68,  76,  77,  107,  111,  114,  115,  116, 
132,  135,  330. 

Ethoxyacrolein  acetal,  with  Hg-aniline, 
216. 

/3-Ethoxy-hydrocmnamic  esters,  from  C-Hg 
cpds.,  314. 

£-Ethoxy-hydrocinnamic  acid,  change  to 
cinnamic  acid,  315. 

«-Ethoxy-phosphenyl  chloride,  from  C-Hg 
cpd.,  267. 

Ethyl  acetate,  catalyst  in  making  R2Hg. 
See  Esters,  as  catalysts. 

Ethyl  acetate,  from  Hg  ethyl  and  acetic 
acid,  42  ;  —  from  Hg  ethyl  and  bromo- 
acetic  ester,  94. 

Ethyl  acetylene,  with  Hg  salts,  119;  — 
alcohol,  from  C-Hg  cpas.  of  acetylene, 
16 ;  —  from  C-Hg  cpds.  of  ethylene, 
32,  45,  108,  110 ;  —  in  making  mer- 
carbides,  14,  19 ;  —  with  bases  and 
Hg  cpds.,  14,  19. 

Ethyl  aniline,  Hg-,  56,  229;  —  anthranilic 
acid,  Hg-,  301 ;  —  bismuth  dichloride, 
from  C-Hg  cpd.,  97  ;  —  bromide,  with 
C-Hg  cpds.,  80. 

Ethylene,  from  bromoacetic  ester  and  Hg 
ethyl,  80,  94  ;  —  from  ethanol  Hg-  cpds. 
and  acids,  108,  109;  —  from  diethyl 
ether  dimercuri  cpds.  and  acids,  111, 
114 ;  —  from  iodoform  and  Hg  ethyl, 
95  ;  —  from  Hg  ethyl  and  cyanides,  77  ; 
— C-Hg  cpds.  derived  from,  20,  32,  45, 
55,  62,  63,  68,  75,  76,  77,  80,  82,  107 1 


118,    141,    310;    —   with    Hg    salts    in 

alcohol,  32,  107,  113;  —  with  Hg  salts 

in   water,   23,   24,    101. 
Ethylene,    with    basic    Hg    salts,    108;    — 

with    mercuric    sulfate,    111 ;    —    C-Hg 

cpds.    with    acids,    32.      See    Acids ;    — 

with    alkyl    halides,    32 ;    —    with    sul- 

fitles,   53. 
Ethylene  diamine,  with  Hg  salts,  370  ;  — 

as   solvent  for  C-Hg  cpds.,  345.     Ethy- 

leue    dibromide,    with    C-Hg    cpds.,    80, 

134,    169,    173,    174;    —    with    sodium 

amalgam,  349 ;  —  as  solvent  for  C-Hg 

cpds.,   203. 

Ethylene  dimercuric   chloride,   53. 
Ethylene  iodohydrine,  from  C-Hg  cpd.,  32, 

68,   108,  110. 

Ethylene,  trichloro;,  with   Hg  salts,  22. 
Ethylenic  cpds.,  with  Hg  salts  in  alcohol, 

120.     See  Unsaturated  cpds. 
Ethyl   hydrazine,   change  to   Hg  ethyl,   92, 

141,   348 ;   —  with    Hg   cpds.,    92,    141, 

348. 
Ethyl    iodide,    with    metallic    Hg,    13;    — 

with  C-Hg  cpds.,  80,  129;  —  with  Hg- 

phenols,  255,  266,  268  ;  —  with  sodium 

amalgam,   14. 

Ethyl  mercapto-  cpds.,  292. 
Ethyl  mercuri-   cpds.,   13,   14,   27,   41,   42, 

52,   63,    65,    67,    68,   80,   81,   83,   84,   91, 

122,  141,  348. 
Ethyl  -  ft  -  naphthylamine  -  6  -  sulf  onic  acid, 

with  Hg  salts,  253. 
Ethyl     phenyl     iodonium     chloride,     from 

C-Hg  cpd.,  81 ;  —  propyl  acetylene,  with 

Hg    salts,    120 ;    —    pyridine,    with    Hg 

salts,    375 ;    —   sulfide,    as    solvent    for 

C-Hg  cpds.,  89. 
Eugenol,   with    Hg  salts,   288 ;   —  methyl 

ether,  with  Hg  salts,  55,  285,  287. 
Explosive   C-Hg    cpds.,    14,    30,    116,    119, 

122,   126,   127,   128,   141,   154,   158,   162, 

273,   362. 

Fats,  as  solvents  for  C-Hg  cpds.,  201. 

Fatty  acids,   Hg-,   131. 

Ferrous  hydroxide,   in  changing  RHgX  to 

KsIIg,  40,  64,  296. 

Fluorescein,  mercuri-,   56,  323;  —  dimer- 
curi-, 321,  323  ;  —  tetramercuri-,  323 ; 

-  dibromo-,  Hg-,  323,  370. 
Fluorides,   with    C-Hg   cpds.,   284. 
Fluorsilicate,  Hg-,  with  acetylene,  69. 
Formaldehyde,  with  Hg  cpds.,   126. 
Formamide,  N-Hg-,  160. 
Formanilide,   N-Hg-,  232. 
Formatemercuri-  cpds.,  43,  175,  181,  201, 

203,   228. 
Formic  acid,   with   C-Hg   cpds.,   168,   198, 

203. 
Formic  ester,   from   C-Hg  cpd.   of  carbon 

monoxide,   34,   138. 
Formic  ester,   Hg-,   55,   70,   81,   137,   138; 

—  Hg-,  with   bases,  49. 
Form-p-toluidide,   N-Hg-,  245. 
Formyl-a-naphthylamine,    N-Hg-,   250. 
French   Patents,   380. 
Fulminate,   Hg-,   343. 
Fulminic    acid,    from    Hg    cpd.    of    nitro 

methane,  16. 

Fumaric  acid,  with  Hg  salts,  32,  151. 
Fumaramide,   N-Hg-,   161. 
Fusion,  reaction  of  Hg  cpds.  with  organic 

substances  without  a  solvent,  234,  235, 

255,   257,   290,   348. 

General   reactions  of  C-Hg  cpds.,   39. 
German  Patents,  378. 


SUBJECT  INDEX 


387 


Glucinum,   with   C-Hg  cpds.,   8k,  94,  100; 

—  alkyls,  from  C-Hg  cpds.,  84,  100  ;  — 

ethyl,  94. 

Glucosides,   with    Hg  cpds.,   332. 
Ghitarimide,  double  cpds.  with  C-Hg  cpds., 

295. 

Glycerol,  with  Hg  cpds.,  374. 
Glycine.      See   Ainino   acids. 
Glycine,    o-carboxyphenyl-,    Hg-,    302 ;    — 

phenyl-.   Hg-.     See  Anilido  acids. 
Glycols,    from    unsattirated    cpds.    by    Hg 

salts,   22,  32,   285. 
Gold,   with   C-Hg  cpds.,   83,   94. 
Gold    crucible    method    for    Hg    analysis, 

365. 

Gooch   filter,    special,  for  Hg  sulfide,   363. 
Grignard   reagent,    in    making   C-Hg   cpds., 

in,  22,  2(5.  29,  39,  89,  92,  173,  174,  1S3, 

184.  185,   188,   200;  —  in  making  mer- 
rurihis-   epVls..    R.IIg,    86,    164;    —    with 
nu'rcuri-ketones,  24,   29,  57,  32'f,  325. 

Guaiacol,    Hg-,   59,   282 ;   —  acetate,   Hg-, 

282. 
Guaiacoxy-acetic   acid,    Hg-,   269. 

Halides.  metallic,  effect  on  C-Hg  linkage, 
57.  58,  73,  76.  280,  281,  291  ;  —  with 
N-Hg  cpds.,  373. 

Halides.    non-metallic,    with    C-Hg    cpds 
16,  40,  78,  166. 

Halogen  acetylenes,  with  Hg  salts,  22 
119. 

a-Halogen  esters,  with  sodium  amalgam, 
28. 

Halogens,  determination  in  C-Hg  cpds 
363;  —  with  C-Hg  cpds..  67,  86,  89, 
93.  100.  102.  103,  104.  105,  148,  165, 
175,  182,  183.  192,  198  202  228  236 
246.  259.  272,  273.  277.  281.'  298,'  316! 
323.  324.  333.  336.  351,  358;  —  with 
X-HJ*  cpds.,  70. 

Heating  C-Hg  cpds.,  79,  83.  84,  87  92 
93.  94,  122.  129,  138.  166.  175,  182 

185.  193,    198,    201,    203,    214;    —    Hg 
salts.    35,    191 ;    -  -    Hg    salts    of    acids 
which      lose     carbon     dioxide     readily 
formation  of  n2Hg,  25,  39,  191,  193  ;  — 
organic   ''mercurous"    cpds ,    112 

Hernin.    Hg-,    356. 

Hemoglobin.    Hg-,    356. 

Heptenol,   dimethyl-,   with    Hg   salts,    329. 

Hermophenyl,    369. 

Heterocyclic  cpds..  containing  Hg  as  a 
member  of  the  ring,  23,  27,  28  52  64 
65,  66,  70.  349;  —  containing  Hg  and 
an  acetylene  linkage,  71  :  —  contain- 
ing Hg  and  oxygen,  47.  48,  54,  60,  62, 
63.  76.  77.  112,  135,  313. 

Hexahydro-phenyl  iodide,  with  sodium 
amalgam,  27,  65. 

c?/r>to-Hexyl  mercuri-  cpds.,   27,   65 

*?-Hexyl  mercuri-  cpds.,  52. 

Hydrargyrol,   369. 

Hydrargyroseptol,   369. 

Hydrargyrum   carbolicum,  254. 

Hydration  of  acetylenic  cpds.,  119.  See 
Acetylene,  Piperonyl  acetylene,  etc. 

Hydrazine,    with    C-Hg   cpds.,    126,    127. 

Hydrazines,  with   Hg   cpds.,   formation   of 

Hydrazine  '  carb'oxylic     ester,     change     to 

N-Hg-C  cpd.,  34,  70,  140. 
Hydrazo  dicarboxylic  ester,  from  Hg  cpd., 

Hydrocinnamic     esters,     /Salkoxyl-,     from 

V'"t*|£    epos.,    54, 
Hydrocyanic  acid,  with  C-Hg  cpds.,  198. 


Hydrogen   analysis   of  C-Hg  cpds.,   361. 
Hydrogen   chloride  gas,   with   C-Hg  cpds., 

167 ;   —  iodide,   with    sodium  amalgam, 

28;  —  peroxide,  with  C-Hg  cpds.,  287. 
Hydrosulfites,     for     changing     RHgX     to 

R2Hg,    64. 
Hydroxy    acids,    with    Hg    salts,    151  ;    — 

amino  benzenes,  Hg-,  59. 
a-Hydroxy-0-amino-isobutyric    salts,     with 

Ilg-salicylic  acid,  368. 
Hydroxy   arsonic  acids,   Hg-,   64 ;  —  azo- 

benzene,  from  C-Hg  cpds.,  258  ;  —  ben- 

zoic  acids  and  esters,  Hg-,  57,  64.     See 

Salicylic  acid. 

w-IIydroxy  benzoic  acid,  Hg-,  319. 
p-Hydroxy  ben/oic  acid,  Hg-,  320,  355. 
Hydroxy  benzyl  alcohol,  mercuri-,  288 ;  — 

dimercuri-,   288. 
jS-Hydroxy    butyric   acid,   from    C-Hg   cpd., 

54,    150;   —   HK-,   150. 
w-Hydroxy   dimetfijlanillne,   Hg-,  59. 
/j-H.vdroxy    hydrociunauiic    acid,    Hg-,    54, 

310  ;  —   from   C  Hg   cpd.,   54,   310. 
Hydroxy  la  mine,  with  C-Hg  cpds.,  126,  156. 
Hydroxymercuri-  cpds.,  15,  49,  67,  88,  94, 

96,  100,    102,    105,    123,    126,    136,    156, 
169,   170,   182,   183,  214,   219,  221,   223, 
225,   227,   229,  231,   232,  233,   234,   236, 
242,   243,  244,   249,   252,   253,   263,   270, 
286,   326,    348. 

o-Hydroxy-p-methyl  anisole,  Hg-,  282. 
Hydroxymethyl  succinic  acid,   Hg-,   151. 
Hydroxy  naphthoic  acids,   Hg-,  321. 
p-Hydroxy-m-nitro-benzyl      alcohol,       Hg-, 

289. 

£-Hydroxy  propionie  acid,  Hg-,  149. 
Hydroxy  succinic  acid,  Hg-,  150 ;  —  sul- 

fobenzoic    acid,    Hg-,    320 ;    —    sulfonic 

acids,   Hg-,   64. 
Hydryl,    357,   369. 

Hypobroniites,  with  C-Hg  cpds.,  126. 
Hypochlorites,  with  C-Hg  cpds.,  126. 
Hypochlorous  acid,  with  C-Hg  cpds.,  168. 

Imidos.  with  C-Hg  cpds.,  319. 
Imidodihydroxamic  acid,   from  C-Hg  cpd., 

18,   88. 
ludandione,  Hg-,  326  ;  —  acetyl,  Hg-,  326  ; 

—  curbethoxy,    Hg-,    326. 

Indole,    Hg-,    342;   --   methyl,    Hg-,    342; 

—  p-anisyl,    Hg-,   342. 

Inner   salts  of  hydroxymercuri   acids,   49. 
Intramolecular    oxidation    and    reduction, 

42,    44,    49,    102. 
Iodide  chlorides,  with  C-Hg  cpds.    81    95 

97.  170,    173,   375. 

Iodides,  in  changing  RFIgX  to  RoHg,  60 
75,  181.  223,  228.  255,  262,  263,  265 
266,  267,  313,  334,  338,  341;  —  'split- 
ting effect  on  C-Hg  linkage,  256,  280, 
291,  298,  310. 

Iodides,  with  C-Hg  cpds.,  39,  51,  60,  73 
75  105,  113,  128,  132,  135,  146,  148 
150,  160,  202,  211,  223,  225  251  252 
258  to  262,  265,  266,  273,  276  283' 
298,  310,  313,  330,  334,  338,  340,'  341; 
-  with  C-IIg.  cpds.  formed  from  un- 
saturated  cpds.,  54,  132,  149,  160;  — 
with  N-Hg  cpds.,  233,  250,  307  ;  —  with 
metallic  Hg,  13,  14,  26;  —  with  sodium 
amalgam.  See  Sodium  amalgam. 

lodimetric    analysis    of    C-Hg    cpds.,    259, 

Iodine,  with  C-Hg  cpds.,  34,  86,  89,  93, 
96,  100  to  106,  110,  114,  123,  135,  139 
147,  165,  174,  175,  184,  198,  200,  209 
236,  246,  259,  272,  277,  281,  298,  316, 


388 


INDICES 


323,   333,   336,   351,   358  ;  —  with  C-Hg 

cpds.  formed  from  unsaturated  cpds.,  46, 

110,  111. 

Iodine  bromide,  with  C-Hg  cpds.,  73 ; 
-  chloride,  with  C-Hg  cpds.,  73;  — 

pentoxide,   from   iodine  and   C-Hg   cpd., 

175. 
p-Iodo-o-acetotoluidide,    from    C-Hg    cpd., 

246. 
lodo-anilines,    from   C-Hg   cpds.,    72,    209 ; 

—  anthranilic  acid,  from  C-Hg  cpd.,  73, 
298. 

o-Iodo-benzoic  acid,   Hg-,   56,   295. 

jModo-4-carboxy-/3-naphthol,  from  C-Hg 
cpd.,  281. 

lodochlorides.     See  Iodide  chlorides. 

lodo-p-cresol,  from  C-Hg  cpd.,  277 ;  — 
cyanogen,  with  C-Hg  cpds.,  86. 

lodoform,  from  C-Hg  cpds.,  69,  70,  106; 
-  with  C-Hg  cpds.,  80,  94,  95,  98. 

lodoformic  ester,  from  C-Hg  cpds.,  70, 
139. 

lodohydrine,   from   C-Hg  cpd.,  46. 

lodo-hydroxy-nitro-benzyl  alcohol,  from 
C-Hg  cpd.,  289. 

lodomethyl  mercuri-  cpds.,  26,  42,  49,  68, 
76,  106. 

a-Iodo-naphthalene,  from  C-Hg  cpd.,  73, 
198. 

Iodo-/3-naphthol  carboxylic  acid,  from  C-Hg 
cpd.,  73  ;  —  p-nitro-phenol,  from  C-Hg 
cpd.,  272,  275  ;  —  nitro-phenol  arsonic 
acid,  from  C-Hg  cpd.,  358  ;  —  phenols, 
from  C-Hg  cpds.,  71  ;  —  phenyl  glycine 
ester,  from  C-Hg  cpd.,  72,  236. 

£-Iodo-propionic  ester,,  with  sodium  amal- 
gam, 22,  28,  147. 

lodo-salicylic  acid,  from  C-Hg  cpd.,  72, 
316  ;  —  thiophenes,  Hg-,  60,  338. 

Iron,  with  C-Hg  cpds.,  83,  93,  166. 

Isatin,   Hg-,   321. 

Isoamyl,  etc.     See  Amyl,  etc. 

Isoapiol,  with  Hg  salts,  285,  287. 

Isocyanates,  formation  by  C-Hg  cpds.,  43, 

Isocyanides,  from  C-Hg  cpds.,  86. 
Isoeugenol    methyl    ether,    with    Hg   salts 

285. 

Isomyristicine,  with   Hg  salts,  285. 
Isosafrole,  with   Hg  salts,   32,   285. 
Itaconic  acid,  with  Hg  salts,  74,  148,  151. 
Keto  acids,  with  Hg  salts,  152. 
Ketones,   from   C-Hg   cpds.,   81,   336,   338 ; 

—  reduction  to  mercuribis-  cpds.,  R2Hg, 
22;  —  Hg-,  30,  57,  155;  —  with  Grig- 
nard  reagents,  24,  30,   57,  324,   325. 

Ketones,  with  Hg  cpds.,  30,  375. 

Lecithin,   Hg-,   149.    ' 

Levulinic  acid,  with  Hg  salts,  152. 

Levurargyre,    369. 

Levuretin,   369. 

Lime  method  for   Hg  analysis,   361. 

Lithium,  with  C-Hg  cpds.,   165. 

Lutidines,  with   Hg  salts,  375. 

Magnesium  ethyl,  from  C-Hg  cpd.,  93  ;  — 

methyl,  from  C-Hg  cpd.,  87  ;  —  phenyl, 

from    C-Hg    cpd.,    166;    —    with    C-Hg 

cpds.,  84,  87,  93,   166. 
Maleic  acid,   with    Hg   salts,   32,   74,   148, 

150. 

Malic  acid,  from  C-Hg  cpd.,  54,  150,  151. 
Malonic  acid  and   ester,   Hg-,   23    30    50 

74,   80,    82,    141,    152. 
Malonic     ester,    sodium    derivative,    with 

Markownikoff's  Rule,   33. 


Medical  Journals,  references,  371. 

Meracetin,   369. 

Morcapto  Hg-  cpds.,   292. 

Mercarbides,  14,  19,  30,  33,  43,  52,  76,  77, 
79,  80,  125,  129,  144,  157,  158,  235. 

Mercuration,  18 ;  —  by  addition  to  un- 
saturated  cpds.,  31  ;  —  by  Grignard 
reagents,  29 ;  --  by  mercuric  acetate, 
34  ;  —  by  mercuric  oxide,  30  ;  —  and 
hydrolysis,  35  ;  —  of  aniline,  17,  210  ; 
-  anisole,  263 ;  —  aromatic  amines, 
theory  of,  220  ;  —  aromatic  cpds.,  34  ; 
-  benzene,  171,  175 ;  —  p-Bromo- 
dimethylaniline,  227  ;  —  dimethyl  ani- 
line, 17 ;  -  -  halogen  acetylenes  and 
ethylenes,  34. 

Mercuration  of  nitro  benzene,  189  ;  —  of 
phenetole,  267  ;  —  quarternary  ammo- 
nium cpd.  of  m-aminophenol,  direct 
formation  of  R2Hg,  275 ;  —  toluene, 
180,  183. 

Mercurials,   Proprietary,   368. 

Mercuribis-  cpds.,  R^Hg,  methods  of  form- 
ation, 40,  59;  —  theory  of  formation 
from  RHgX,  60 ;  —  from  arsenoxides 
and  Hg  cpds.,  213;  --  formation  by 
bases,  64  ;  —  by  cyanides,  92  ;  —  by  di- 
rect mercuration  of  quarternary  ammo- 
nium cpds.  of  m-amino-phenol,  274  ;  —  by 
ferrous  hydroxide,  40,  64  ;  —  from  the 
free  radicals,  RHg-,  23  ;  —  by  heating 
formatemercuri-  cpds.,  228  ;  —  by  heat- 
ing Hg  salts  of  organic  acids  which 
lose  carbon  dioxide  easily,  25,  39,  191, 
193 ;  —  by  hydrosulfites,  64 ;  —  by 
metallic  iodides,  39,  75,  223,  228,  255, 
256,  265,  266,  338,  341 ;  —  by  metals, 
40,  60,  64,  65,  334,  340  ;  —  by  reducing 
agents,  271,  275,  282,  295,  317  ;  —  by 
sodium  amalgam,  28,  200 ;  —  spon- 
taneously from  RHgl,  334. 

Mercuribis-  cpds.,  R2Hg,  preparation  ;  — • 
by  sulfides,  17,  40,  51,  56,  91,  173,  177, 
213,  214,  222,  230,  231,  234,  292,  318, 
358  ;  —  by  sulfocyanates,  40,  61,  256  ; 
—  by  organic  sulfur  cpds.,  65,  178  ;  — 
by  sodium  stannite,  328.  See  Stan- 
nites ;  —  by  sodium  thiosulfate,  17,  178, 
234,  250,  260  ;  —  by  zinc  alkyls,  65. 

Mercuribis-  cpds.,  R2Hg,  with  Hg  salts, 
40,  65,  88,  95,  104,  105,  113,  168,  169, 
174,  183,  185,  199,  204,  224,  225,  237, 
261,  262,  335,  351. 

Mercuri-naphthols,  with  diazonium  salts, 
3.r>4  ;  —  phenols,  with  diazonium  salts, 
354. 

Mercuric  oxide,  in  making  C-Hg  cpds.,  30; 

-  salts,    with    R2Hg    cpds.      See    Mer- 
curibis- ;   —  double   cpds.   with   aniline, 
206;  —  with  N-Hg  cpds.,  208;  —  sul- 
flde,  quantitative  filtration,  363. 

Mercurization,   18.      See   Mercuration. 

Mercurochrome-,  220,  370. 

Mercurol,  370. 

Mercurophen,  370. 

Mercurous  acetate,  22  ;  —  chloride,  change 

to    mercuribis-    cpds.,    91 ;    —    organic 

cpds.,   62,   64,   112,   135. 
Mercury  analysis  of  C-Hg  cpds.,  361,  363. 
Mercury  di-amyl,  etc.     See  Amyl  Hg-,  etc. 
Mercury,    with    alkyl    iodides,    13,    14,    89, 

91,   98,   104 ;   —   with   allyl    iodide,    14, 

26,  122  ;  —  with  propargyl  iodide,  123  ; 

-  from  C-Hg  cpds.   and  acids,  24,   87, 
94,  104  ;  —  from  C-Hg  cpds.  and  bases, 
176;    —   from    C-Hg    cpds.    by    heating, 
182.     See  Heating  C-Hg  cpds. 


SUBJECT  INDEX 


Mercury  dyes,   24,   212,   355. 

"Mercury-N-isodiacetate,"    308. 

Mercury    telluride,    from    C-Hg    cpd.,    167. 

Mergal.  369. 

Meriodin,  368. 

Merlusan,   370. 

Meta   position,   avoidance  of,   by  mercury, 

35. 
Metals,   with   C-Hg   cpds.,   60,    64,    65,    83, 

86,    93,    100,    102,    103,    142,    165,    198, 

309,   334,   340,  361.     See  Mercuribis-. 
Metals,     complex,     KHg-.       See     Complex 

metals. 

Methane,   from   C-Hg  cpd.,   87. 
Methine   trimercuri-   cpds.,    106. 
Methacetin,    N-Hg-,    233. 
Methyl  acetylene,  with  Hg  salts,  16,   119; 

-  alcohol,    with    Hg    cpds.,    126,    374; 

—  aniline,  Hg-,  56,  221,  300  ;  —  w-butyl 
acetylene,   with    Hg  salts,   120  ;   —  cin- 
namate,   with   Hg  salts  in  alcohols,   23  ; 

-  chavicole,     Hg-,    285  ;    —    diphenyl 
amine,    Hg-,    61,    235. 

Methyl  ethyl  acrolein,  from  C-Hg  cpd., 
134. 

Methyl  ethyl  ketone,  from  C-Hg  cpd.,  119  ; 
-  reduction  to  R2Hg,  22,  102;  —  tri- 
mercuri-, 119,  158. 

Methyl  ethyl  pyridine,  with  Hg  salts,  375  ; 

—  glyoxime,   from   C-Hg   cpd.,   69,   157  ; 

-  indole,    Hg-,    342;    --    iodide,    with 
C-Hg  cpds.,  81,  115,  138  ;  —  with  C-Hg 
cpds.    formed    from    unsaturated    cpds., 
115  ;  —  with  metallic  mercury,  13.    See 
Mercury  ;   —  with   Hg-anilines,   81,   214, 
221,  224,  230,  231  ;  —  with  Hg-phenols, 
81,  263,  265;  —  with  sodium  amalgam, 
14,   27. 

Methyl  isocyanate,  preparation  by  C-Hg 
cpd.,  43 ;  —  ketole,  Hg-,  343  ;  —  ma- 
Ionic  ester,  Hg-,  50,  146,  152,  153 ;  — 
mercaptan  with  Hg-benzoyl  chloride, 
294. 

Methyl  mercuri-  cpds.,  13,  18,  26,  27,  29, 
41,  52,  64,  65,  67,  76,  77,  78,  83,  84, 
85,  86,  88,  89,  90,  106. 

2 -Methyl- jr-phthalyl-indole,    343. 

Methyl  piperonyl  ketone,  from  C-Hg  cpd., 
195  ;  —  pyridines,  with  Hg  salts,  375  ; 
—  sulfide,  as  solvent  for  C-Hg  cpds.,  89  ; 

-  thienyl   ketone,  from  C-Hg  cpd.,   82, 
"334. 

Methylene    chloroiodide.    from    C-Hg    cpd., 

68  ;  —  iodide,  with   Hg,  26,   105. 
Methylene,  Hg-,  26,  76,  80,  105,   106,  120. 
o-Methoxybenzoic  acid,   Hg-,   320. 
;>-Methoxybenzoic  acid,   Hg-,  320. 
/S-Methoxy   hydrocinnamic   esters,   from    C- 

Hg   cpds.,    46,   312,   313 ;   —  acid,    Hg-, 

60;  —  ester,  Hg-,  311. 
p-Methoxyphenyl     phosphorus     dichloride, 

263. 

Mesaconic  acid,   with    Hg  salts,    151. 
Mesitylene,    Hg-,   187. 
Mesityl  oxide,  with   Hg  cpds.,  158. 
"Mixed"    mercurv    cpds.,    R-Hg-R',    24,    29, 

92,   97,   174,   184. 
Miscellaneous     double      cpds.      containing 

mercury,    references,   376. 
Miscellaneous  references,   371.   376,   377. 
Molecular    addition    cpds.,    107,    119,    198, 

3-12;  —  from      unsaturated      cpds.,      24, 

32. 
Molecular   weight  determinations   of  C-Hg 

cpds.,    134. 
Monobromo-acetylene,     119 ;     -   -     benzene, 

with   sodium  amalgam,  28. 


Monochloro-acetamide,  N-Hg-,  160 ;  — 
acetylene,  from  C-Hg  cpd.,  119  ;  —  Hg-, 
34,  69,  119. 

Monoethyl-aniline,  229. 

Monohalogen    acetylenes,    Hg-,    56,    119. 

Monomethyl-aniline,    Hg-,    221. 

Morpholine,  from  C-Hg   cpd.,   111. 

Myristatemercuri-  cpds.,   176. 

Myristic  acid,   with   C-Hg  cpds.,   168. 

Myristicin,   Hg-,  285. 

Naphthalene  cpds.,  with   Hg  salts,  24,  36. 
Naphthalene,  Hg-,   197.      See  Naphthyl-. 
a-Naphthalene     diazonium     nitrate,     from 

C-Hg  cpd.,   199  ;  —  sulfonic  acid,   Hg-, 

203. 

0-Xaphthalene    sulfonic   acid,    Hg-,    204. 
Naphthionic  acid,   Hg-,   251. 
a-Naphthol,   Hg-,   18,  44,   58,  76,  276,  279, 

280. 

£-Xaphthol,   Hg-,  20,   58,   279,   280,   354. 
Naphthols,  Hg-,  with  diazonium  salts,  354. 
0-Xaphthol   carboxylic   acid,   Hg-,   73,   280, 

355. 
a-Xaphthol-4-sulfonic  acid,  with  Hg  salts, 

58,    281;    --    5-sulfonic    acid,    with    Hg 

salts,    281. 
£-Naphthol-6' -sulfonic  acid,  with   Hg  salts, 

281.   355. 
jS-Xaphthol-3,    6-disulfonic    acid,    with    Hg 

salts,  282. 

Naphthoxyacetic  acid,   Hg-,  269. 
a-Naphthylamine,  Hg-,  57,  76,  250,  251. 
0-Naphthylamine,  Hg-,  58,  251. 
o-Naphthylamine-.'/-sulfonic    acid,    Hg-,    57, 

251  ;  —  5-sulfonic  acid,  dimercuri-,  252, 

253,  356  ;  —  with  diazotized  Hg-aniline, 

212. 
j3-Xaphthylamine-6-sulfonic   acid,    Hg-,    58, 

253.   355. 

a-Naphthyl    bromide,    with    sodium    amal- 
gam.   14,   197,    202. 
/3-Xaphthyl    chloride,    from    a-naphthylmer- 

curi-    cpd.,    79,    199 ;    -  -    with    sodium 

amalgam,  202. 
a-Naphthyl    dichloro     arsine,     from     C-Hg 

cpd.,    199. 
0-Xaphthyl     dichloro    arsine,     from    C-Hg 

cpd.,    203. 
Naphthyl    halidcs,   with    sodium   amalgam, 

28. 
a-Naphthyl    iodide,    from    C-Hg    cpd.,    198, 

202. 
a-Naphthyl   Hg-   cpds.,   14,   29,   57,   64,   66, 

73,  78.  79,  80,  84,  92,  197,  199,  201. 
0-Naphthyl  Hg-  cpds.,  66,  194,  202,  203. 
X-Bromo-acetamide,   with   C-Hg  cpds.,   43, 

170. 

N-Chloro-acetanilide,  with  C-Hg  cpds.,  170. 
X-Halogen  acid  amides,  with   C-Hg   cpds., 

170. 

"Xinety-nine,"   370. 
"X-isodiacetate,"    308. 
Xitratemercuri-   cpds.,    99,    101,    110,    123, 

126,   128,   134,   142,   143,   158,   168,   177, 

179,   182,   183,   184,   193,   199,   202,  217, 

245,   250.   331. 
Xitric  acid,   with   C-Hg  cpds.,  43,   45,  47, 

52,    127.    128,    138,    141,    145,    147,    168, 

182,  193,  198,  235,  284,   318,   340. 
Xitric  oxide,  with  C-Hg  cpds.,  168,  182. 
Xitriles,  with  Hg  salts,  374. 
Xitritemercuri-   cpds.,   154,    192. 
Xitro-acetamide,     N-Hg-,    160 ;    —    acetic 

ester,    Hg-,   51,   69,    74,    11,8. 
o-Xitro-aniline,    mercuri,    221 ;    —    dimer- 
curi-, 221  ;  —  with  Hg  salts,  220. 


390 


INDICES 


m-Nitro-aniline,   mercuri-,   221 ;  —  dimer- 

curi-,  221. 
p-Nitro-aniline,    mercuri-,    221 ;   —   dimer- 

curi-,  221 ;  —  with  Hg  salts,   220. 
o-Nitro-aniline  arsonic  acid,  Hg-,  357  ;  — 

benzal    halides,    from    C-Hg    cpds.,    72, 

192  ;  —  mercuri-  cpds.,   191. 
o-Nitro-benzaldehyde,  from  C-Hg  cpds.,  72, 

192. 
Nitro-benzene,  from  C-Hg  cpds.,   43,  190; 

—  Hg-,  71,  189  ;  —  with  Hg  salts,  19, 
35. 

Nitro-benzene  sulflnic  acids,  with  Hg  salts, 

190. 
p-Nitro-benzoyl  chloride,  with  C-Hg  cpds., 

334. 
o-Nitro-benzyl    Hg-    cpds.,    191,    193;    — 

benzoic  acid,  Hg-,  295,  299. 
w-Nitro-benzoic  acid,  Hg-,  296. 
i>-Nitro-benzoic  acid,  from  C-Hg  cpd.,  193  ; 

—  Hg-,  296,  307. 
Nitro   cpds.,    Hg-,    123. 
/>-Nitro-diethylaniline,  with  Hg  salts,  220, 

231. 
o-Nitro-dimethylaniline,     with     Hg     salts, 

220,   229. 
rn-Nitro-dimethylaniline,    with     Hg    salts, 

220,   229. 
inNitro-dimethylaniline,     with     Hg     salts, 

220,   228. 

Nitro-ethane,    Hg-,    61. 
p-Nitro-ethylaniline,    with    Hg    salts,    220, 

230. 

Nitroform,  Hg-,  123. 
jj-Nitro-guaiacol,    Hg-,    282. 
p-Nitro-guaiacol   acetate,   Hg-,   282. 
Nitro-methane,    Hg-,    16. 
p-Nitro-methylaniline,  with  Hg  salts,  220, 

222. 

Nitro-naphthalene,    from    C-Hg    cpd.,    198. 
o-Nitro-phenol,  Hg-,  270,  271,  370. 
j>-Nitro-phenol,    Hg-,    22,    56,    62,    75,    270, 

271,   272. 
Nitro-phenol   arsonic  acids,   Hg-,   62,  358 ; 

-   sulfonic  acids,   Hg-,   370. 
o-Nitrophenyl  Hg-  cpds.,  43,  189. 
m-Nitrophenyl  Hg-  cpds.,  190. 
p-Nitrophenyl  Hg-  cpds.,  190. 
Nitro-benzene  sulflnic  acids,  with  Hg  salts, 

190. 
p-Nitrophenyl   thienyl   ketone,    from   C-Hg 

cpd.,  334. 

Nitro-resorcin,   Hg-,   283. 
5-Nitro-salicylic  acid,  Hg-,  319. 
Nitro-toluenes,    Hg-,    44,    49,    51,    72,    182, 

191,    193,    374. 
Nitrogen    cpds.,    organic,    cpds.    with    Hg 

salts,   375. 
Nitrogen    tetroxide,    with    C-Hg   cpds.,    88, 

168,    179,    182,    184,    199. 
Nitrogen    trioxide,    with    C-Hg    cpds.,    18, 

168,   179,    182,   184,    199. 
Nitrosamines,    Hg-,    221. 
Nitroso-amino-benzene,   Hg-,   218 ;  —  ben- 
zene, from  C-Hg  cpds.,  168;  —  phenol, 

Hg-,   218,   256. 

o-Nitroso-toluene,    from    C-Hg    cpds.,    179. 
^-Nitroso-toluene,       from        C-Hg       cpds., 

182. 
Nitrous  acid,  with  Hg-methylaniline,  221 ; 

-   with    Hg-phenols,   256. 
N-Hg    cpds.,    from    Hydrazine  .carboxylic 

ester,    34. 

N-Hg  cpds.,  miscellaneous,  59,  65,  70,  140, 
159,  162,  178,  205,  207,  208,  220,  221, 
232,  245,  249,  250,  296,  303,  304,  307, 
308,  321,  373  (Bibliography). 


N-Hg   cpds.,    with    benzoyl    chloride,    245 ; 

—  with  carbon  disulfide,  208;  —  with- 
iodides,  233  ;  —  with  Hg  salts,  208  ;  — 
with  sulfur  cpds.,  208. 

Novasurol,    370. 
"No.    99,"    370. 

Nucleic  acids,  Hg-,  356,  369,  370  ;  —  with 
C-Hg  cpds.,  319. 

n-Octyl  Hg-  cpds.,  27,  67,  105. 

defines,  with   Hg   cpds.,   107. 

Oleic  acid,   with   Hg  salts,   149,   150. 

O-Hg  cpds.,   254. 

Organic    halides,    change    to    C-Hg    cpds., 

26.  See  Mercury,  Sodium  amalgam,  etc. 
Orsudan,   Hg-,  369. 

Oxalatemercuri-   cpds.,   99,   101,    156,   331. 
Oxamide,   N-Hg-,   161. 

Oxidation  by  mercuribis-  cpds.,  87  ;  —  by 
Hg  salts,  21,  24,  32,  109,  116,  117,  126, 
154,  194,  207,  253,  282,  284,  332. 

Oxides,  organomercuric-,  232,  258,  261, 
265,  268. 

Oxidizing  agents,  with  C-Hg  cpds.,  88,  94, 
96,  169,  171,  182,  183,  188. 

Oxygen  acids,  with  C-Hg  cpds.,  45,  110. 
See  Nitric  acid  and  Sulfuric  acid. 

p-Oxyphenyl   ethyl   amine,   Hg-,    275. 

Parabanic   acid,   with   C-Hg  cpds.,   319. 
Patents,  378. 

Patents  on  acetylene  with   Hg   salts,   376. 
cj/cZo-Pentadiene,   with   Hg  salts,  120. 
iso-Pentane,   from  C-Hg  cpds.,   104. 
Pentamethyl   benzene,   Hg-,   28,   187. 
Pentamethylene,    dimercuri-,    29,     52,     64, 
70,  351  ;  —  iodide,  from  C-Hg  cpds.,  70  ; 

-  halides,    with    sodium   amalgam,   23, 

27,  351. 

Pentamethyl  phenyl  Hg-  cpds.,  28,  187. 
Perchlorate  Hg-  cpds.,  128. 
Perchloro-ethane,  from  C-Hg  cpd.,  69,  121. 
Permanganates,  with   C-Hg   cpds.,   88,   94, 

96,   126,   134,   169,   171,   182,  183. 
Pharmaceutical   Journals,   references,   371. 
Pharmacological  studies,  references,  371. 
Plienacyl   bromide,   from   C-Hg  cpd.,   324 ; 

—  halides,   with    sodium    amalgam ;    — • 
Hg-  cpds.,  28,  30,  35,  44,  50,  51,  72,  324; 

-  Hg-   cpds.,    with   Grignard    reagents, 
324. 

Phenanthrene,    Hg-,    36. 

Phenegole,   370. 

Phenetole,    Hg-,    66,    78,    266,    267.      See 

Phenetyl. 

p-Phenetyl,  antimony-,  with  Hg  cpds.,  268. 
o-Phenetyl   Hg-   cpds.,    255,    266. 
p-Phenetyl  Hg-  cpds.,  28,  267,  268. 
Phenols,  acetyl-,  Hg-,  75. 
Phenol    ethers,     Hg-,    261.       See    Anisole, 

Phenetole,   etc. 
Phenol,    Hg-,    18,    35,    43,    47,    49,    56,    61, 

62,    64,   71,   75,   81,   254,  259,   263,   265, 

266,    268,    276,    354. 
Phenols,    Hg-,   from    Hg-anilines,    355  ;   — 

with   diazonium    salts. 
Phenol,    as   solvent   for   C-Hg   cpds.,    256 ; 

—  with   diazotized    Hg-aniline,   212. 
Phenolates,   with   Hg   salts,   254,   257. 
Phenol   arsonic  acids,    Hg-,    357,    358 ;    — 

ethers,    allyl    cpds.    of-,    with    Hg    salts, 

22,    284;    —    propenyl    cpds.    of-,    with 

Hg   salts,   284. 
Phenols,     nitro-,     Hg-,     22.       See     Nitro- 

phenols. 
Phenol-phthalein,     Hg-,     321 ;    —    trimer- 

curi-,    256,    322. 


SUBJECT  INDEX 


391 


Phenols,    substituted,    Hg-,    269. 

Phenol  sulfonic  acids,   Hg-,   64,  279,  369  ; 

-  disulfonic   acid,    Hg-,    279,    369 ;    — 
sulfonephthalein,  trimercuri-,  321,  322  ; 
— •  — -  tetramercuri-,  322. 

Phenosafranine,  Hg-,  58. 
Phenoxyacetic  acid,  269. 
Phenyl  acetate,  Hg-,  75,  255,  256,  260, 

261,    265. 
Phenyl    acetic   acid,    from   C-Hg   cpd.,    93 ; 

—  acetylene,  with  Hg  salts,  33,  56,  69, 
194;    —    acetylide,    Hg-,    197;    —    ar- 
seuious   oxide,    with    Hg   salts,    164;   — 
sulfide,  with   C-Hg  cpds.,   95. 

Phenyl  boric  acid,  with  Hg  salts,  17,  171 ; 
—  bromide,  with  sodium  amalgam,  163  ; 

-  chloride,   from   C-Hg   cpds.,   167 ;  — 
dichloro    arsine,    from    C-Hg    cpds.,    78, 
167,   176 ;   —  dichloro   phosphine,   from 
C-Hg   cpds.,    41,    183.      See   Phosphenyl 
chloride. 

Phenyl  ethyl  iodonium  chloride,  from  C-Hg 
cpd.,  81  ;  —  glycine  ester,  Hg-,  72,  236  ; 

-  hydracrylic   acid,    from    C-Hg    cpds., 
54,   310 ;   —  hydrazine,   with    Hg   cpds., 
141,  164,  348  ;  —  iodide  chloride,  with 
C-Hg  cpds.,   81,   95,   97,   170. 

Phenyl  Hg-  cpds.,  15,  16,  22,  29,  37,  41, 
43,  56,  61,  62,  64,  65,  66,  71,  78,  80, 
82,  83,  84,  141,  163,  165,  171,  172,  173. 
248  ;  —  with  arsenic  trichloride,  16  ;  — 
with  nitrogen  oxides,  18  ;  —  with  phos- 
phorus trichloride,  16 ;  —  with  silicon 
tetrachloride,  16. 

Phenyl  propiolic  ester,  with  Hg  salts. 
316. 

0-Phenyl   propionic  acid,   Hg-,   309. 

Phenyl  silicon  trichloride,  from  C-Hg  cpd., 
16,  166 ;  —  succinamide,  N-Hg-,  161 ; 

—  thienyl   ketone,   from   C-Hg  cpd.,   82, 
334,    336 ;    —   thiophene,    Hg-,    336 ;   — 
thiourea,  with  phenyl  white  precipitate, 
209  ;  —  p-tolyl   chloro   phosphine,   from 
C-Hg    cpd..    183 ;   —   white    precipitate, 
72,    208,   211,    215. 

Phloroglucin,    Hg-,    283. 

Phorone,    Hg-,    158. 

Phosgene,    with    C-Hg   cpds.,    82. 

Phosphatemercuri-    cpds.,    99. 

Phosphenyl  chloride,  from  C-Hg  cpds.,  16, 
41,  78,  167,  183. 

Phosphine,  phenyl  dichloro-.  See  Phos- 
phenyl chloride. 

Phosphorus  tribromide,  with  C-Hg  cpds., 
78,  122  ;  —  trichloride,  with  C-Hg  cpds., 
16,  40,  78,  87,  88,  167,  179,  180,  224, 
263,  267. 

Phthalic  acid,  with  Hg  salts,  21,  290,  321. 

Phthalimide,   N-Hg-,   321. 

Physiological  salt  solution,  with  C-Hg 
cpds.,  309. 

Picolines,   with   Hg   salts,   375. 

Picrates  of  C-Hg  cpds.,   113,   127. 

Picric  acid,   Hg-,  273. 

Pinene,  with'Hg  salts,  332. 

Piperazine,  with  C-Hg  cpds.,  319. 

Piperidine,  with  Hg  salts,  375  ;  —  with 
C-Hg  and  N-Hg  cpds.,  140. 

Piperidyl   urethane,   from   N-Hg  cpd.,    140. 

Piperonyl  acetylene,  with  Hg  salts,  195. 

Poison  mercury  cpds.     See  Toxic. 

Polymers  of  C-Hg  cpds.,  24,  28,  64,  120, 
143.  144,  152.  154,  157,  211,  239,  351. 

Polymercuri-benzenes,   35,    169. 

Polysulfides,    with    C-Hg    cpds.,    127,    128. 

Potassium  with  C-Hg  cpds.,  165. 

Potassium  iodide,  etc.     See  Iodides,  etc. 


Preparation  of  organomercuric  cpds.,  gen- 
eral, 26  ff. 

Propanol   Hg-   cpds.,   115. 

Propargyl  iodide,  with  metallic  Hg,  26, 
123. 

Propargyl  Hg-  cpds.,  26,  123  ;  acetal,  with 
Hg-aniline,  213,  216. 

Propenyl.cpds.,  with  Hg  salts,  22,  32,  284. 

Propional  dehyde,  from  C-Hg  cpds.,  134. 

Propionamide,   N-Hg-,  161. 

Propionates,   change   to   mercarbides,    129. 

Propionatemercuri-  cpds.,  176,  181,  264, 
268. 

Propionic  acid,  a-Hg-,  31,  50,  H6t  153; 
—  £-Hg-,  22,  147,  168;  —  with  C-Hg 
cpds.,  268 ;  —  ester,  0-iodo-,  with  so- 
dium amalgam,  28 ;  —  £-Hg-,  70. 

/3-M-propoxy-hydrocinnamic  acid,  from  C- 
Hg  cpd..  315  ;  —  ester,  Hg-,  315. 

0-j'so-propoxy-hydrocinnamic  acid,  from  C- 
Hg  cpd.,  315;  —  ester,  Hg-,  315. 

Proprietary  mercurials,  368. 

?so-Propyl   acetylene,   with   Hg   salts,   119. 

Propyl    alcohol,   with    Hg   cpds.,    126. 

iso-Propyl   alcohol,   with   Hg  cpds.,   125. 

Propyl   arsine,    tri-,   from   C-Hg   cpd.,   78; 

-  benzene.   187. 

iso-Propyl   ether,   Hg-,   115,    116. 
n-Propyl  iodide,  with  C-Hg  cpds.,  81,  139. 
iso-Propyl    iodide,    with    metallic    Hg,    67 ; 

-  separation   from  allyl  iodide,   123. 
iso-Propyl   ketone,   from   C-Hg   cpds.,    119. 
n-Propyl  phenyl  Hg-  cpds.,  28. 

Propyl  phosphine,  fri-,  from  C-Hg  cpds., 
78  ;  —  pyridine,  with  Hg  salts,  375. 

«-Propyl  Hg-  cpds.,  15,  27,  67,  78,  84, 
99. 

iso-Propyl   Hg-  cpds.,   22,   27,    101. 

Propylene,  with  Hg  salts,  32,  115;  — 
glycol,  from  C-Hg  cpds.,  134;  —  Hg-, 
131.  133. 

Propylene   oxide,    Hg-,    132. 

Providol,    259,   370. 

Pyramidone,    Hg-,    349. 

Pyrazole,    Hg-,    345,    348. 

Pyrazoline,    Hg-,    55. 

Pyrazolones,  Hg-,  23,  36,  45,  51,  55,  343, 
348. 

Pyridine,  catalyst  in  changing  RoHg  to 
R-R  and  Hg,  193  ;  —  cpds.  with  C-Hg 
cpds.,  272 ;  —  effect  on  tetramercuri- 
diphenylamine,  235  ;  —  homologs,  with 
Hg  salts,  375  ;  —  Hg-,  342  ;  —  as  sol- 
vent for  C-Hg  cpds.,  52,  124,  157,  172, 
174,  183,  188,  200,  244,  271,  272,  274, 
326,  352,  362 ;  —  with  Hg  salts,  375. 

Pyridine.      See   Dinitro-phenyl-. 

Pyrimidines,    Hg-,    348. 

Pyrocatechin,  with  Hg  salts,  282 ;  — 
acetic  acid,  Hg-,  269,  369 ;  —  mono- 
methyl  ether,  59,  282 ;  —  o-carboxylic 
acid,  from  C-Hg  cpd.,  72. 

Pyrrole,  with   Hg  salts,  375. 


Quarternary  ammonium  salts,  Hg-,  72, 
226,  230,  232,  374. 

Quinazolines,    Hg-,    349. 

Quinone-imide-acinitro-Hg    salts,    220. 

Quinom   Hg  cpds.,  214,  221,  280. 

Quinoid   structure   of   Hg-nitrophenols,   22. 

Quinoline,  Hg-,  343 ;  —  salts  of  diiodo- 
diethyl  ether,  112 ;  —  with  Hg  salts, 
375 ;  —  carboxylic  acid,  Hg-,  343 ;  — 
hydroxy  carboxylic  acids,  Hg-,  343 ;  — 
sulfonic  acids,  Hg-,  343. 

Quinosol,    Hg-,   369. 


392 


INDICES 


Radicals,   RHg-,   preparation,   23. 

Reducing  agents,  alkaline,  in  changing 
RHgX  to  R2Hg,  40,  64,  271,  282,  295, 
296,  299,  307,  317,  320. 

Reduction  of  C-Hg  cpds.,  34,  126,  192, 
255,  328,  329,  332,  361. 

References,  miscellaneous,  371. 

Replace  carboxyl  group  by  Hg,  25,  39, 
191,  193,  290. 

Resins,    Hg-,    332. 

Resorcinol,  mercuri-,  59 ;  —  dimercuri-, 
283 ;  —  with  diazotized  Hg-anilines, 
212 ;  —  benzeneazo-,  Hg-,  355  ;  —  di- 
methyl ether,  Hg-,  59. 


Saccharin,   Hg-,  308,  309. 

Safranines,   Hg-,  349. 

Safrole,   with    Hg   salts,    22,    32,    55,    285, 

286,   287. 

Salicylate,   "basic  mercury,"  316. 
Salicylic    acid,    Hg-,    56,    57,    58,    72,    73, 

309,  316,  354,  368,  369  ;  —  Hg-,  soluble 

double  cpds.,  59,   318. 
Salicyl    alcohol,    Hg-,    288;    —    aldehyde, 

with   Hg-aniline,   212  ;   —  arsonic  acid, 

Hg-,   320,  369. 

Salicylic  ester,   Hg-,  61,  62,  317. 
Salicyloxyacetic    acid,    Hg-,    269. 
Salicyl  sulfonic  acid,   Hg-,   369. 
Saligenin,   Hg-,  288. 
Salts  of  aniline  with   Hg  cpds.,   205. 
Schiff's  bases,   mercuri-,   212. 
Schotten-Baumann     reaction     with     C-Hg 

cpds.,   82,   110,   255,   258,   273,   277. 
sec-Alkyl  Hg-  cpds.,  22,  27. 
sec-Iodides,  with   sodium  amalgam,  27. 
Silicon  tetrachloride,  with  C-Hg  cpds.,  16, 

166,  182. 
Silver,  with  C-Hg  cpds.,  83,  94  ;  —  oxide, 

in    changing    RHgX    to    R2Hg,    172;   - 

salts,    with    C-Hg   cpds.,   41. 
Soda  lime,  with   C-Hg  cpds.,  198,  203. 
Sodium,    in    making    R2Hg,    64,    83,    334 ; 

—  with  C-Hg  cpds.,  64,  81,  83,  86,   93, 
103,  165,  334,  340,   361. 

Sodium  acetoacetic  ester,  with  RHgX,  41  ; 

—  amalgam,    in    making   R2Hg,    64,    85, 
91,  164,  174,  200  ;  —  with  amino  cpds., 
28 ;  —  with   bromides,    14,    15,    17,   26, 
27,    28,    163,    179,    180,    181,    186,    187, 
191,   197,   202,   204,   223,   231,   245,   262, 
263  ;  —  with  C-Hg  cpds.,  145,  165,  175, 
201  ;    —    with    chlorides,    28,    202 ;    — 
with    chloroformic    ester,    15  ;    —    with 
dibromides,   23,   24 ;    —  with   dihalides, 

27,  350  ;  —  with  a-halogen  esters,  28  ; 

-  with   hydrogen   iodide,   28 ;   —  with 
hydroxyl  cpds.,  28  ;  —  with  iodides,  27, 

28,  99,    101,    103,    105,    189;    --   with 
0-iodopropionic  ester,  22  ;  —  with  nitro 
cpds.,  28  ;  —  with  phenacyl  halides,  28  ; 

—  with  unsaturated  halides,  28. 
Sodium  carbonate,  with  C-Hg  cpds.,   298  ; 

-  ethyl,   from    C-Hg   cpd.,   84,    93,    95; 

—  iodide,  with  C-Hg.     See  Iodides;  — 
iso-amyl,     from     C-Hg     cpd.,     103 ;     — 
malonic     ester,     with     RHgX,     41 ;     — 
methyl,  from  C-Hg  cpd.,  86  ;  —  phenyl, 
from   C-Hg   cpd.,    166 ;   —  sulflde,    with 
C-Hg    cpds.      See    Sulfides ;    —    thiosul- 
fate.      See  Thiosulfates. 

Soluble   cpds.   of   Hg-salicylic   acid,   319. 

Sozoiodol,   Hg-,  368. 

Splitting  C-Hg  linkage  by  bases,  261 ;  — 
by  chlorides,  253 ;  -  -  by  diazonium 
salts,  258,  261.  See  Diazo- ;  —  by 


metal   halides,   76 ;   —   by   iodides,    223, 
252,   256,   258,  259,  276. 

Stability   of  C-Hg  linkage,   39. 

Stannic  chloride,  with  C-Hg  cpds.,  166. 

Stannites,  in  making  RaHg,  40,  77,  112, 
164,  176,  262,  263,  328  ;  —  with  C-Hg 
cpds.,  62,  63,  114,  135,  294,  358. 

Stannous  chloride,  with  C-Hg  cpds.,  77, 
87,  255,  296  ;  —  iodide,  tripropyl-,  with 
C-Hg  cpds.,  100. 

Starch,  with  Hg  cpds.,   126,  131. 

Sublamin,    370. 

Succinic  acid,  hydroxy,  Hg-,  from  maleic 
acid,  54  ;  —  with  C-Hg  cpds.,  153. 

Succinamide,  N-Hg-,  161. 

Succinimide,   N-Hg-,   161. 

Succinyl  chloride,  with  C-Hg  cpds.,  82. 

Sugar,   with    Hg  cpds.,   131. 

Sulfamido  benzole  acids,  Hg-,  59,  307, 
319 ;  —  Hg-,  double  cpds.  with  C-Hg 
cpds.,  309. 

Sulfanilic  acid,  Hg-,  250. 

Sulfatemercuri-  cpds.,  99,  101,  128,  193, 
217,  222,  331. 

Sulfhydrates,    organomercuric-,    110,    128 ; 
—   in   making   R2Hg,   56,    224,   226;    - 
with   C-Hg  cpds.,   215,   222. 

Sulfides,  ammonium-,  solvent  for  C-Hg 
cpds.,  52;  --  poly-,  with  C-Hg  cpds., 
52  ;  —  organomercuric-,  40,  50,  51,  54, 
56,  57,  91,  96,  99,  110,  114,  116,  117, 
127,  128,  129,  136,  138,  140,  175,  177. 
189,  201,  294,  317 ;  —  organic-,  addi- 
tion cpds.  with  C-Hg  cpds.,  90  ;  —  as 
solvents  for  C-Hg  cpds.,  89  ;  —  in  mak- 
ing R2Hg,  17,  61,  91,  164,  173,  175, 
213,  222,  223,  225,  229,  231,  233,  293, 
294,  318.  358  ;  —  with  C-Hg  cpds.,  40, 
50,  55,  56,  59,  61,  122,  123,  126,  128, 
132,  141,  149,  151,  153,  155,  162,  173, 
174,  190,  192,  200,  201,  202,  213,  214, 
243,  247,  251,  252,  253,  261,  273,  278. 
280,  281,  282,  286,  287,  292,  293,  298, 
304,  307,  309,  310,  313,  314,  316,  317, 
323,  324,  325,  331,  342,  344,  345,  346, 
347,  348,  349,  354,  355,  356,  357,  358, 
359  ;  —  with  C-Hg  cpds.  formed  from 
cinnamic  ester,  46;  —  with  C-Hg  cpds. 
formed  from  ethylene,  46. 

Sulfides,  with  C-Hg  cpds.  formed  from 
various  unsaturated  cpds.,  33,  46,  54, 
55,  132,  286,  312,  313,  315;  --  with 
N-Hg  cpds.,  59,  243,  304,  307,  308,  342, 
373. 

Sulfites,    with    C-Hg   cpds.,    284. 

Sulfine  chlorides,  from  C-Hg  cpds.,  224. 

Sulfinic  acids,  in  making  C-Hg  cpds.,  22, 
37,  171,  190,  193.  203. 

Sulfobenzide,  from  C-Hg  cpd..  167. 

Sulfocyanatemercuri-,  177,  202,  227,  265, 
268. 

Sulfocyanate  determination  of  mercury, 
363. 

Sulfocyanates,  in  splitting  C-Hg  linkage, 
256 ;  —  in  making  RsHg,  40,  61,  181, 
266,  267. 

Sulfocyanogen,  with  C-Hg  cpds.,  166,  177. 

Sulfones,    from    C-Hg   cpds.,    82,    167. 

Sulfone  chlorides,  with  C-Hg  cpds.,  82, 
167. 

Sulfonic  acids  of  benzidine,  with  Hg  salts, 
349  ;  —  of  naphthalene,  with  Hg  salts, 
203  ;  —  of  phenol,  Hg-,  64. 

Sulfonyl  chloride,  with  C-Hg  cpds., 
83. 

Sulfosalicylic  acid,   Hg-,  56,  369. 

Sulfur,  with  C-Hg  cpds.,  169,  176,  177. 


SUBJECT  INDEX 


393 


Sulfur  cpds.,  with  Hg  salts,  374,  376;  — 

with  N-Hg,  208  ;  —  dioxide,  with  C-Hg 

cpds.,   168. 
Sull'uric    acid,    with    C-Hg    cpds.,    44,    90, 

147,   198,  301. 

S-Hg   cpds.,    161,    292,    293,    373. 
Sulfur  monochloride,  with  C-Hg  cpds.,  79, 

127,   129. 

Sulfurous  acid,  with  C-Hg  cpds.,  126. 
Sulfur  trioxide,  with  C-Hg  cpds.,  168. 
Sunlight,  action  with  C-Hg  cpds.,  13,  26, 

90,  91,  98,  104.. 
Swedish  Patents,  380. 
Swiss   Patents,   379. 


Tartramide,   N-Hg-,   161. 

Tartrateinercuri-   cpds.,   100. 

Tartronic  acid,   with   Hg   salts,   152. 

Tellurium,  with  C-Hg  cpds.,  94 ;  —  di- 
chloride,  with  C-Hg  cpds.,  167  ;  —  ethyl, 
94. 

Tellurides,    with    Hg   salts,   376. 

Terpine,   Hg-.     See  Terpinol. 

Terpineol,  with  Hg  salts,  33,  326,  328,  329. 

Terpinol,    Hg-,   326,    327. 

Tertiary  alcohols,  from  C-Hg  cpds.,  24, 
30,  57,  324  ;  —  with  Hg  salts,  125. 

Tertiary  halides,   with   C-Hg  cpds.,   335. 

Tetra-brorao-thiophene,  from  C-Hg  cpd., 
73  ;  —  methylerie  diiodide,  with  sodium 
amalgam,  27,  350 ;  —  nitro  dibenzyl, 
from  C-Hg  cpd.,  193. 

Theobromine,  Hg-,  58,  162. 

Theophylline,    Hg-,    58,    162. 

Theory,  electronic-,  applied  to  C-Hg  cpds., 
24,  42  ;  —  of  mercuration  of  aromatic 
amines,  220 ;  —  of  formation  of  mer- 
curibis-  cpds.,  60. 

Thermal  decomposition  of  C-Hg  cpds.,  83, 
84,  87,  92,  93,  94,  122,  138,  166,  175, 
182,  185,  193,  198,  201,  203. 

Thienones  from  C-Hg  cpds.,  82,  333,  334, 
338. 

Thienyl  chloro  arsines,  from  C-Hg  cpds., 
79,  334. 

Thienyl  ketones,  from  C-Hg  cpds.,  82,  333, 
334,  338;  —  with  Hg  salts,  375. 

Thienyl  Hg-  cpds.  See  Thiophene ;  — 
methvl  ketorie,  82 ;  —  phenyl  ketone, 
82.  * 

Thiocarbanilide,   in   making  R2Hg,   65 ;   — 

from    N-Hg    cpds.,    208;    —    with    C-Hg 

cpds.,    164 ;   —  with   N-Hg   cpds.,   208 ; 

-   with   phenyl   white  precipitate,   209. 

Thiocyanates,  in  making  R2Hg,  40,  61, 
181,  266,  267. 

Thiocyanatemercuri-  cpds.,  177,  202,  227, 
265,  268. 

Thiocyanate  method  for  mercury  analy- 
sis, 363. 

Thiocyanates,  in  splitting  the  C-Hg  link- 
age, 256. 

Thiocyanogen,  with  C-Hg  cpds.,  166,  177. 

Thionyl  chloride,  with  C-Hg  cpds.,  79, 
167,  199,  224,  291,  292,  294. 

Thiophene,  Hg-,  18,  36,  45,  58,  60,  64,  67, 
73,  78,  79,  SO,  82,  83,  333,  336;  — 
dimercuri-,  335,  336 ;  —  removal  from 
benzene  by  mercuric  acetate,  335. 

Thiophene,  a-substituted,  Hg-,  36,  336;  — 
a-phenyl-,  Hg-,  336 ;  —  a  a'-dimethyl-, 
Hg-,  36,  339  ;  —  0-methyl-,  Hg-,  340 ; 
—  0-isopropyl-,  Hg-,  341  ;  —  ^'-di- 
methyl-, Hg-,  341 ;  —  carboxylic  acid, 
Hg-,  336. 

Thiophenol,  from  C-Hg  cpd.,  170. 


Thiosulfates,  in  making  R2Hg,  17,  40,  61, 

178,   181,   213,   221,   234,  244,   245,   249, 

260,  261,  266,  299,  318. 
Thiosulfatemercuri-  cpds.,  61,  213,   217. 
Thiosulfates,    with    C-Hg    cpds.,    235,    284, 

298  ;  —  with  N-Hg  cpds.,  233,  250,  373. 
Thioureas,   in   making   RaHg,   65,   164 ;   — 

with  C-Hg  cpds.,  65,  164,  178  ;  —  with 

N-Hg  cpds.,   208. 

Thiourea,  tetra    (phenylmercuri-),  178. 
Thymol,   Hg-,   278  ;  —  dimercuri-,  278. 
Thymoxy-acetic    acid,    Hg-,    269. 
Tin,     with    C-Hg    cpds.,     166,     170,    198. 

See  Stannous,  etc. 

Tolane,    dinitro-,    from    C-Hg   cpd.,    192. 
Toluene,    from    Hg   benzyl   and    acid,    24 ; 

-  mercuration  of-,  35,   182. 
o-Toluene    diazonium    nitrate,    from    C-Hg 

cpd.,  179. 
p-Toluene   diazonium    nitrate,    from    C-Hg 

cpd.,  182. 
p-Toluene    sulfinic    acid,    change    to    C-Hg 

cpd.,    181,    182. 
p-Toluene     sulfone     chloride,     with     C-Hg 

cpds.,    83,    167,    182. 

o-Toluic  acid,  Hg-,  56,  309.  368  ;  —  chlo- 
ride, with  C-Hg  cpds.,  334. 
p-Toluic   acid    chloride,    with    C-Hg    cpds., 

334. 

Toluidides,   Hg-,   23,  245. 
Toluidines,  with   Hg  salts,   23. 
Toluidine,    Hg-,    61,   241. 
o-Toluidine,   double    salts    with    Hg    cpds., 

242 ;   —   mercuri-,    241  ;   —  dimercuri-, 

241. 
m-Toluidine,    dimercuri-,    242;   —    trimer- 

curi-,  242'. 
p-Toluidine,   double    salts   with    Hg   cpds., 

244  ;  —  'mercuri-,  243. 
o-Toluidine  arsonic  acid,   Hg-,  357,  369. 
Toluidoacetic  acids.      See  Tolyl  glycine. 
o-Tolyl   boric   acid,   change   to   C-Hg   cpd., 

179. 
m-Tolyl  boric  acid,   change  to  C-Hg  cpd., 

180. 
p-Tolyl   boric   acid,   change   to   C-Hg   cpd., 

182. 
o-Tolyl   boron  dichloride,   from   C-Hg  cpd., 

179. 
p-Tolyl  boron  dichloride,  from  C-Hg  cpd., 

182. 
o-Tolyl   dichloro   arsine,    from    C-Hg   cpd., 

179. 
p-Tolyl   dichloro   arsine,    from    C-Hg    cpd., 

182. 
o-Tolyl    dichloro    phosphine,     from     C-Hg 


cpd.,    179. 
i-Toly 


m-Tolyl     dichlorophosphine,     from      C-Hg 

cpd.,    180. 

o-Tolyl  glycine  ester,  Hg-,  247  ;  —  dimer- 
curi-,   247. 
m-Tolyl   glycine   ester,    Hg-,   248;   —   tri- 

mercuri-,    248. 

p-Tolyl    glycine    ester,    Hg-,    248. 
o-Tolyl   iodide   chloride,   with   C-Hg   cpds., 

170. 
p-Tolyl   iodide   chloride,    with   C-Hg   cpds., 

170. 
Tolyl  Hg-  cpds.,  15,  28,  29,  56,  71,  78,  83, 

179. 

o-Tolyl  Hg-  cpds.,  78,  179. 
m-Tolyl    Hg-    cpds.,    180. 
p-Tolyl    Hg-    cpds.,    15,    78,    181,   183. 
Tolyl  phenyl  chloro  phosphine,  from  C-Hg 

cpd.,  78. 
p-Tolyl     silicon     trichloride,     from     C-Hg 

cpds.,   182. 


394 


INDICES 


o-Tolyl  thieriyl  ketone,  from  C-Hg  cpds., 
334. 

p-Tolyl  thienyl  ketone.  from  C-Hg  cpds., 
334. 

Toxic  C-Hg  cpds.,  86,  93,  97,  98,  128,  165, 
370. 

Trans  isomers  of  unsaturated  acids,  with 
Hg  salts,  23,  32,  149,  310. 

Trans  terpinol,  Hg-,  329 ;  —  from  C-Hg 
cpd.,  329. 

Tribromo  ethylene,  Hg-,  121  ;  —  phenol, 
Hg-,  270 ;  —  thiophene,  from  C-Hg 
cpd.,  73. 

Trichloro  ethylene,  Hg-,  69,  121 ;  —  with 
Hg  cpds.,  34. 

Trichloromercuri   acetaldehyde,    42. 

Trihalogen    ethylenes,    Hg-,    22,   55. 

Trimethyl  benzene,  Hg-,  187 ;  —  benzole 
acid,  Hg-,  309 ;  —  phenyl  ammonium 
hydroxide,  with  Hg  salts,  220  ;  —  eth- 
ylene, Hg-,  117 ;  —  phenyl  Hg-  cpds., 
28 ;  —  pyridines,  with  Hg  salts,  375. 

Trimethylene  'dibromide,  with  sodium 
amalgam,  349. 

Trinitro  benzole  acid,  Hg  salt  of-,  effect 
of  heat,  25. 

Trinitro   phenol,    Hg-,   273. 

Trinitro   phenyl   Hg-  cpds.,   25,   191. 

Triolein,    with    Hg    salts,    149. 

Triphenyl  antimony  dichloride,  from  C-Hg 
cpds.,  167 ;  —  arsihe,  167 ;  —  guani- 
dine,  from  phenyl  white  precipitate, 
209 ;  —  from  N-Hg  aniline,  208 ;  — 
methane,  from  C-Hg  cpds.,  79,  169  ;  — 
stibine,  from  C-Hg  cpds.,  171. 

Tripropyl  stannic  iodide,  with  C-Hg  cpds., 
100. 

Tyrosine,  Hg-,  58,  321,  370. 

United  States  Interdepartmental  Social 
Hygiene  Board,  365. 

U.   S.  Patents,   379. 

Unsaturated  acids,  with  Hg  salts,  74,  80, 
119,  148;  —  alcohols,  with  Hg  salts, 
131  ;  —  amines,  with  Hg  salts,  374. 

Unsaturated  cpds.,  with  Hg  salts  in  al- 
cohol; 23,  32,  77,  120,  149,  314,  344 ; 
—  with  Hg  salts  in  water,  20,  23,  24, 
31,  32,  33,  34,  36,  45,  47,  48,  53,  55,  62, 
75,  77,  107,  137,  194,  204,  284,  309, 
312,  326,  329,  331,  339,  344,  348. 

Unsaturated  cpds.,  Hg  cpds.  derived  from-, 
with  reducers,  284  ;  with  sulfides,  55. 


Unsaturated  halides,  with  Hg,  26,  56,  lii', 
-  with  Hg  cpds.,  34  ;  —  with  sodium 
amalgam,  28. 

Upsalan,    370. 

Urea,   with   I-Ig   cpds.,   161,   319,   374. 

Urethane,  from  Hg  cpd.  formed  from  car- 
bon monoxide,  34,  70  ;  —  from  Hg  cpd. 
formed  from  hydrazine  carboxylic  ester, 
70  ;  —  with  C-Hg  cpds.,  319. 

Uric  acid,    Hg-,    162. 

Vanillin,   Hg-,   323. 

Veratric  acid,    Hg-,   321. 

Veronal,    Hg-,    161,    370;    --    with    C-Hg 

cpds.,   269,   312,   319,   370. 
Vinyl    cpds.,    107;    --    alcohol,    Hg-,    131, 

154  ;    —   bromide,    Hg-,   121. 
Violuric   acid,    Hg-,    161. 
Volatile  C-Hg  cpds.,  43,  63,  98,   104,   109, 

128,   162,    165,    181,    183,   262,   264. 

Water-soluble  C-Hg  cpds.,  58,  90,  161,  269, 

295,   312,   319,   368. 
White  precipitate,  phenyl-,  208,  211,   215. 

Xanthine  bases,   with   Hg   salts,   319. 

Xylenes,    Hg-,   186. 

o-Xylene,    Hg-,    186. 

m-Xylene,    Hg-,    186. 

p-Xylene,   Hg-,  187. 

p-Xylenol,    Hg-,    278. 

p-Xylenoxy-acetic  acid,   Hg-,  269. 

Xylidines,   Hg-,  250. 

Xylyl  Hg-  cpds.,  28,  78,   186,  187. 

Yeast,   with   Hg   salts,   369. 

Zinc,  with  C-Hg  cpds.,  84,  87,  93,  97,  100. 
102,  104,  166,  198  ;  —  with  ethyl  mer- 
curic hydroxide,  96 ;  —  alkyls,  from 
C-Hg  cpds.,  84,  100 ;  —  with  C-Hg 
cpds.,  85,  91,  97,  98  ;  —  with  Hg  salts, 
96  ;  —  aryls,  from  C-Hg  cpds.,  84  ;  — 
ethyl,  65,  93,  122  ;  —  isoamyl,  104  ;  — 
isobutyl,  102  ;  —  methyl,  87  ;  —  phenyl, 
166 ;  —  propyl,  100. 

Zinc  and  bases,  with  C-Hg  cpds.  formed 
from  unsaturated  cpds.,  284,  285,  286, 
288. 

Zirconium,  with  C-Hg  cpds.,  94,  166;  — 
chloride,  with  C-Hg  cpds.,  172,  179  ;  — 
phenyl,  166. 


AUTHOR'S  INDEX 


Abelmann,  A.,   24,  57,  324,   325,  361,  3G4. 
Acree,   S.  F.,  83,  166. 
Allen,   348. 

Andre".   G.,   160,   205,   209,   249. 
Anschutz,   R.,  364. 
Aronbeim,    B.,   167. 

Auld.    S.   M.,   22,   51,   69,   71,   75,    82,   154, 
157,   158,   161,   270,   272,  307,   324,   325. 

Balbiano,  L.,  21,  55,  117,  284,  285  to  288, 

331. 

Balestra,  E.,   151. 
Bamberger,  E.,  18,  44,  88,   168,  177,  279, 

280. 

Bandrowski,    F.,   251. 
Bauermeister,  M.,  64,  73,  82,  83,  333,  335, 

336,   339,    343. 

Bauerschmidt,   H.,  45,  51,  55,  363. 
Becker,   P.,   78,   166,   171,   182. 
B£hal,   A.,   120. 
Behrend,    R.,    152. 
Biginellic,   P.,    118. 
Biilraann,  E.,  20,  23,  50,  54,  74,  107,  131, 

134,   141,   142,   148,   150,   152,   155,   158, 

309,   363. 

Biltz,  H.,  55,  68,  69,  118,  119,  194,  195. 
Blasi,   N.,  79,  171,   172,   176,   190,   265. 
Blumentbal,    F.,    57,    296,    299,    300,    307, 

319,  320,   355,   356. 
Boebringer,   348. 

Bonitsch.  G.,  210.  213,  216,  218,  255,  355. 
Bogert,   M.   T..   349. 
Brame,  J.   S.   S.,  43,  118. 
Brandes,  R.,   361. 
v.    Braun,    J.,   23,   349. 
Breest,   F.,   107,    109. 
Brieger,   R.,   24,   57,   58,   73,   76,  203,   217, 

251,   259,   276,   280,   316,   321,   362,   364. 
Briining,  A.,   151. 
Bucbner,  E.,  51,  70,   80,  83,  162. 
Buchtala,   H.,   318,  319,  321. 
Buckton,  G.  B.,  13,  65,  67,  77,  78,  83,  84, 

85,   86,    87,   88,    89,   90,   91,   92,   93,   94, 

96,  98. 

Burkard,  E.,  118. 
Buroni,  G.,   316. 
Byk,  A.,   209. 

Cahours,  A.,  15,  78,  84,  93,   99,   100,   101. 

Calmels,   G.,   86. 

Cambi,  170. 

Campisi,  C.,  184. 

Chalkley,    L.,    Jr.,    43,    59,    71,    190,    194, 

Chapman,  E.  T.,  67,  83,  84,  86,  91,  93. 

Chattaway,    F.    D.,    202. 

Colombo,    83,    188. 

Cowper,  R.,   125,   364. 

Crymble,  C.   R.,  86,  88,  89,  92,  97,  98. 

Curtius,  E.,   162. 

Deniges,   G.,   20.   116,    117,    125,    152,   155, 

158,   207,    333. 
de  Plato,   G.,   160. 


Desesquelle,   E.,   18,  254,   257,   258,   279. 

Dessaignes,  V..   159,   161. 

Devillers,   L.,   295. 

Dhar,  N.,  249. 

Diels,   O.,   34,   70.    140. 

Dimroth,  O.,  18,  20,  44,  51,  56,  57,  61,  62, 
63,  64,  66,  71,  72,  81,  82,  125,  141,  176, 
180,  183,  189,  194,  209,  210,  211,  212, 
213,  214,  215,  217,  225,  234,  254,  255, 
257,  258,  259,  260,  261,  262,  263,  264, 
265,  267,  275,  280,  290,  316,  324,  325, 
335,  353,  354,  364. 

Ditmar,  M.,  52,  62,  67,  86,  89. 

Doepping,    O.,    153. 

Dreher,  E.,  15,  43,  56,  62,  64,  66,  71,  80, 
83,  84,  163,  164,  165,  168,  169,  171, 
172,  175,  181,  184,  191. 

Dunhaupt,  F.,  13,  52,  67,  88,  89,  92,  96, 
97,  98,  364. 

Dufournel,   307. 

Duppa,  D.  F.,  14,  65,  67,  83,  84,  85,  86. 
87,  89,  91,  92,  93,  95,  96,  103,  104, 
361,  364. 

Eichler,  E.,  67,   105. 
Ehrhard,   164. 
Engelhardt,    H.,   151. 
Engelmann,    M..    318,    319. 
Erdmann,   118,   361,   364. 

Feigel,   H.,   52,   79,   125. 

Finzi,   B.,   79,    333. 

Fischer,  B.,   89,   162,   165,   159. 

Fischer,  E.,  22,.  70,  92,  97,  140,  141,  147, 

164,   348. 

Fleck,    H.,   84,   87,    166. 
Fleming-Struthers,    R.    J.,    73,    125,    158, 

330,  324,  325. 

Forster,  C.,  93,  205,  208,  209,  210,  211. 
Foster,  J.,   164,   165. 
Fourneau,   E.,   62,   271,   274. 
Francesconi,   L.,   160. 
Franchimont,  A.,  79,  169. 
Frangois,  206. 
Frankland,  E.,   13,   14,  17,  22,  52,   65,  67, 

83,   84,   85,    86,   87,    88,    89,   90,    91,   92, 

93,  95,  96,  97,  98,  103,  104,  361,  364. 
Franklin,  E.  C.,  160,  210,  249. 
v.  Furth,  O.,  210. 

Gadamer,  J.,  316. 

Gajewski,  326. 

Gavron,    356. 

Genssler,  O.,  47,  48,  77,  115,  116,  141,  145, 

156,   204,  364. 

Gerhardt,  C.,  125,  155,  215,  362. 
Gerngross,  O.,   317,  364. 
Gibson,  C.   S.,   1»,  78,   183,   184. 
Glinsky,    121. 
Godchaux,   E.,  79,   224. 
Goldacker,  P.,  72,  236,  238. 
Graeff,   F.,   167. 

Grignard,   V.,    24,   57,   324,   325,   261,   364. 
Grigorowitch,  156. 

395 


396 


INDICES 


Grote,    K.,    161. 

Griittner,    G.,    15,    24,    52,    64,    65,   70,   71, 

83,  84,  92,  165,  166,  173,  174,  184,  188, 

200,    349,    362,    364. 
Grutzner,  B.,   159,  257. 

Haas,    J.,    47,    55,    56,    69,    119,    194,    195, 

196,    364. 
Hale,  91,  92. 

Hanke,  M.,  47,  62,  63,  261,  358. 
Hantzsch,  A.,  22,  51,   69,  71,   75,   82,   154, 

157,  158,   270,   272,   324,   325,   326,   356. 
Hart,   M.   C.,   288,   363. 
Hasenbaumer,  J.,  167. 

Heidelberger,  M.,  211,  212,  221,  241,  355. 

Heumann,   K.,   79,   167,   173,   199. 

Hilpert,  S.,  15,  24,  52,  62,  64,  65,  67,  70, 
71,  83,  84,  86,  89,  92,  165,  166,  173, 
174,  184,  200,  349,  362,  364. 

Hirschfelder,   A.    D.,   288,    363. 

Hoff,   234. 

Hofmann,  A.   W.,   13,   205,   209,   361. 

Hofmann,  F.,  321. 

Hofmann,  K.  A.,  14,  19,  20,  22,  42,  43, 
45,  48,  52,  53,  55,  56,  69,  76,  77,  78,  79, 
80,  81,  107,  110,  115,  116,  117,  118, 
119,  120,  121,  125,  129,  131,  132,  133, 
134,  141,  142,  144,  146,  152,  154,  155, 

158,  207,  254,  362. 

Howe,  L.   F.,   181,  194,  203,  223,   265. 
Hueter,   R.,  57,   61,   73,   76,  292,  296,   300. 
Hunter,  W.  H.,  270. 

Jackson,  C.  L.,  221. 

Jacobs,   W.  A.,   211,   212,   221,  241,   355. 

Jacobsohn,  220,  228,  230. 

Jacobson,    O.,    187. 

Jermolajeff,   M.,    160. 

Jones,   L.    W.,   15,    16,   24,   42,    66,   85,   87, 

91,  94,  103,  123,   168,   173,   184. 
Jowett,   357. 

Reiser,  E.   H.,   69,  118. 

Kekule",  A.,  79,   169. 

Kelbe,    199. 

Kerb,  J.,  161. 

Kersasp,   H.,   317,   364. 

Kharasch,  M.  S.,  21,  24,  25,  37,  43,  45, 
47,  59,  61,  62,  63,  71,  170,  185,  190, 
191,  193,  194,  218,  220,  228,  230,  235, 
256,  261,  274,  289,  296,  309,  358. 

Khotinsky,   E.,   180,   185. 

Kieseritzky,    R.,   162. 

Kirmreuther,  H.,  22,  56,  69,  78,  119,  121, 

Kissel,  H.,  123,  124,  161. 

Klein,   O.,   206,   242,   244,   251. 

Kochlin,   79,   167,   173,   199. 

Konig,   W.,   343. 

Kothner,  P.,  118. 

Kohn,   M.,   363. 

Kolmer,  J.  A.,  356. 

Krafft,   F.,   165,   167. 

Kraus,  C.  A.,  23,  88,  96. 

Kropat,   K.,    362. 

Kunz,   J.,    179,   182,   200. 

Kurssanow,    N.,    189. 

Kutscheroff,  M.,  16,  81,  118,  119,  121,  363. 

Lachowicz,   B.,   222,   242. 

La  Coste,   95,   167,   179,»181,  182. 

Ladenberg,  A.,  16,  163,  165,  166,  179,  181, 

Lajoux,  H.,  319. 
Lami,  P.,  161. 
Landolt,   H.,   87. 
Landsberg,   M.,  161,  321. 


Lasserre,  A.,   154,  155. 

Launoy,  L.,   271,   274. 

Le   Comte,   O.,   118. 

Lederer,    K.,    363. 

Leeds,    244,   251. 

Levaditi,  C.,  274. 

Ley,   H.,   89,   97,   123,   124,   151,   152,    159, 

160,   162,  165. 

Leys,  A.,  150,  155,  158,  282,  332. 
Liese,  E.,  57,  248,  296,  303. 
Link,   167. 

Linnemann,   E.,   50,   67,   79,   92,   122. 
Lippmann,   E.,   80,    94,    97,   152. 
Lohr,  P.,  84,  86,  87,  92. 
Loloff,  C.,   264,  268. 
Lommen,  220. 
Lumifire,   A.,    279. 
Lyons,    R.,    165,    167. 

Maddrell,    R.,    151. 

Maguire,  J.  A.,  69,  118. 

Manchot,  W.,  24,  47,  55,  56,  69,  81,  107, 
110,  118,  119,  137,  194,  195,  196,  198, 
262,  263,  265,  267,  268,  277,  284,  286, 
•  287,  288,  362,  364. 

Marchand,   R.   F.,   361,   364. 

Markownikoff,    W.,    160. 

Marquardt,   A.,    84,    101,    103. 

Marsh,  J.  E.,  73,  125,  158,  324,  325,  330. 

Marvel,   C.   S.,  29,  86. 

Maynard,   J.    L.,   90. 

McClelland,  N.  P.,  165,  185. 

McFarland,   B.   W.,  232,  233.  245,   250. 

Meharg,  V.  E.,  248,   296,  365. 

Melamed,   180,   185. 

Menschutkin,   N.,    160,   161. 

Meyer,   V.,   16,    123,   187. 

Michaelis,  A.,  16,  17,  43,  66,  78,  79,  95, 
152,  163,  166,  167,  171,  172,  179,  180, 
181,  182,  186,  187,  188,  197,  199,  203, 
204,  223,  224,  262,  263,  264,  265,  267, 
268. 

Middleton,  E.  B.,  39,  47,  49,  61,  75,  149, 
160,  255,  256,  257,  258,  259,  260,  261, 
262,  263,  265,  266,  267,  268. 

Mitchell,    352,    354. 

Mories,   57,   66,   80,   83,   84,   197,   198,   199. 

Montecchi,   G.,   208. 

Moulin,    A.,    348. 

Miiller,  50,  57,  58,  86,  93,  97,  295,  320. 

Mumm,  O.,   68,  118,   119. 

Nardacci.   55. 

Nef,  J.  U.,  16,  123,  154,  195,   197. 

Nicholson,   E.   C.,   364. 

Nieuwland,  J.   A.,   69,   118. 

Norvak,   J.,   161. 

Nunez,  91,  92. 

Nyberg,   B.,   51,   69,   123. 

Odling,   W.,  84,  87,  93. 

Oppenheim,  A.,  16,  78,  82,  91,  122,  152, 
155,  160,  233,  296,  299,  300,  307,  320, 
355,  356. 

Ostersetzer,  A.,   363. 

Otto,  R.,  14,  15,  43,  52,  56,  57,  62,  64,  65, 
66,  71,  73,  80,  83,  84,  85,  90,  91,  98, 
163,  164,  165,  167,  168,  169,  171,  172, 
174,  175,  181,  182,  183,  184,  191,  197, 
198,  199,  201,  202. 

Paolini,    V.,    21,    117,    284,    285,    286,    287, 

331. 

Paterno,   E.,   83,   188. 
Peakes,   221. 
Perkin,  W.  H.,  119. 


AUTHOR'S  INDEX 


397 


Pesci,  L.,  17,  21,  56,  57,  61,  62,  65,  66, 
72,  75,  81,  161,  169,  177,  205,  208,  209, 
210,  211,  212,  213,  214,  215,  217,  221, 
223,  224,  225,  226,  231,  233,  234,  243, 

244,  245,  249,   290,   292,   294,   321. 
Peters,  W.,  22,  93,  166,  171,  179,  182,  190, 

194,  203,  321,  326. 
Petterson,  L.,  50,   74,   159. 
Pfaff,    S.,   160,   233. 
Pfeiffer,   P.,    22,    164. 
Pfliiger,  E.,  161. 

Piccard,   J.,   24,   45,   61,   218,   235,   256. 
Piccinini,   L.,   56,   62,   210,   211,    213,   214, 

217,  233. 
Pigorini,   231. 
Plimpton,   R.  T.,  69,  118. 
Poleck,    131. 

Pope,  W.  J.,  15,  78,  183,  184. 
Prager,  W.,  123,  148,  160. 
Pringsheim,  363. 

Prussia,   L.,   61,   233,   234,   249,   250. 
Purvis,    J.    E.,    165,   185. 

Rabinerson,  J.,  66,  223,  263,  264,  265. 
Raiziss,    G.    W.,    250,    253,    270,    271,    272, 

275,   280,   282,   283,  295,   309,  319,   349, 

356,   357,   358,   359. 
Ray,  P.  C.,  206,  244,  249. 
Reese,  163,  167,  172. 
Reinkober,  K.,  55,  69,  118,  194,  195. 
Reissert,  A.,  44,  45,  51,  72,  191,  194. 
Reitzenstein,   F.,   210,  213,   215,  216,  218, 

243,  244,   255,   354. 
Reynolds,  J.  E.,  15,  155,  158. 
Reynoso,  A.,  125. 
Rilliet,   123. 

Roeder,  G.,  79,  171,  172,  176,  190,  265. 
Rossi,   234. 
Rother,    72,    82,    194,    220,    241,   242,    243, 

245,  250,   275,   302,   307. 
Rudolph,  C.,  72,  209. 
Rupp,   E.,   57,   362. 
Ruspaggiari,  G.,  62,  81,  210,  214. 

Sachs,   G.,  57,  79,  83,  290,   292,  293,   294. 

Sakurai,  J.,  42,   68,   76,   80,  106,  362. 

Sand,  J.,  20,  28,  45,  47,  48,  55,  62,  63, 
64,  68,  70,  76,  77,  81,  107,  109,  110, 
111,  112,  113,  115,  116,  117,  125,  131, 
132,  133,  134,  141,  144,  145,  156,  158, 
204,  284,  290,  326,  361,  362,  364. 

Schaefer,   K.,   159,   160,   162. 

Schamberg,   J.   F.,   271,   352. 

Saytzeff,   121. 

Scheitlin,   E.,   348. 

Schenck,   A.,   223,   233. 

Schiff,  H.,  205,  206,  207. 

Schlenk,   W.,   86. 

Schoeller,  W.,  22,  23,  47,  49,  50,  54,  55, 
57,  58,  60,  61,  62,  68,  70,  72,  73,  76, 
80,  82,  86,  93,  97,  113,  125,  137,  141, 
146,  148,  150,  152,  160,  236,  238,  241, 
243,  245,  248,  292,  293,  294,  295,  296, 
2<J9,  300,  303,  305,  311,  312,  314,  317, 
318,  319,  320,  332,  361,  362,  364. 

Scholl,   R.,  51,  69,  123. 

Schorigin,   P.,    83,   84,   87,   93,   104. 

Schorlemmer,   C.,   14,   94. 

Schrauth,  W.,  22,  23,  45,  47,  49,  50  51 
54,  55,  57,  58,  60,  61,  62,  68,  70,  72 
80,  82,  86,  93,  97,  125,  137,  141,  146 
148,  150,  152,  160,  236,  238,  241,  243, 


245,   248,   292,   293,   294,   295,  296,   299, 

300,   303,   305,   311,   312,   314,   317,  318, 

320,    332,    343,    361,   362,    363,    364. 
Schroeder,   H.,   89,   97,   165,   198. 
Schulemann,   W.,   24,   57,   58,   73,   76,   203, 

217,   251,   276,   280,   321,   362,   364. 
Schulte,   95,    199. 
Scwalbe,    C.,   335,   336. 
Schwarze,   F.,   167. 
Seidel,   88,   89,   94,   96. 
Seller,   E.,   77,   120. 
Sell,  E.,  80,  94,  97. 
Selnii,   13,   125. 
Sestini,    F.,   161. 
Singer,   F.,   28,   48,   64,   70,   107,   110,   115, 

204,   290,   326,   362. 
Smiles,  S.,  90. 
Smith,    C.   E.,    352,    354. 
Sneed,  M.  C.,  90. 
Sobrero,  13,   125. 
Soderback,  E.,  71,   165,  177. 
Stamm,  G.,  213,   215,  243,  244. 
Staronka,   W.,  206. 
Steinkpf,    W.,   64,    66,   67,    73,   79,    82,    83, 

168,   171,   173,   183,  200,   333,   335,   336, 

339,   340. 

Stieglitz,  J.,  47,  62,  63,  261,  358. 
Stoehr,  C.,  113,  132,  136. 
Storey,   T.  A.,  365. 
Strecker,  A.,  13,  90,  97,  98,  99,  160. 
Struensee,   R.,   47,   54,   60,    125,   150,   311, 

312,   313,  314,   364. 
Suida,   W.,   80,   94,   98,   169. 
Swan,  205. 

Tafel,  J.,  22,  67,  101,  102,  158. 
Thiele,   J.,   120. 
Thummel,  K.,  131. 
Torrey,  H.  A.,  270. 
Travers,  M.  W.,  69,  118. 
Truskier,  P.,  22,  164. 

Uthemann,  S.,  34,  70,  140. 

Vauquelin,   153. 

Vecchiotti,   L.,   48,   72,   82,   219,   243. 
Vila,  A.,  62,  271,  274. 
Vohl,  H.,  206. 

Volhard,  J.,  18,  45,  58,  73,  80,  82,  83, 
333,  335,  336,  340,  363. 

Wagner,   H.,  125. 

Weehuizen,  F.,   349. 

Weiner,   89. 

Weller,   J.,   186. 

Werder,   361. 

Werner,   L.,   42,   66,   184,   244. 

Wertheim,   T.,   361. 

Wheeler,  H.  L.,  232,  233,  245,  256. 

White,  E.  C.,  256,  321,   362,   363,  364. 

Whitmore,  F.  C.,  39,  47,  49,  60,  61,  65, 
66,  75,  149,  160,  181,  194,  203,  223, 
227,  248,  255,  256  to  263,  265  to  268, 
296,  362,  363. 

Willgerodt,   C.,   81,   95,   97,   170,   173. 

Wislicenus,   J.,   208. 

Witt,   O.,   74. 

Wolff,   P.,   15,   66,   184. 

Wurtz,   A.,    15,   163,   165,   181,   184. 

Zeiser,   W.   C.,  93,  179,   181. 
Zinin,   N.,   14,   122,   205,   251. 


HC" 


A9T3 


14  DAY  USE 

RETURN  TO  DESK  FROM  WHICH  BORROWED 

BIOLOGY  LIBRARY 

TEL  NO.  642-2532 

This  book  is  due  on  the  last  date  stamped  below,  or 
on  the  date  to  which  renewed. 


Renewed  books  are  subject  to  immediate  recall. 

•-*  .^ 

LD21A-6m-9,'73 
(R2491slO)476-A-32 


General  Library 

University  of  California 

Berkeley 


U.C.  BERKELEY  LIBRARIES 


COEbDS^lb 


